Results
Exhaustive Search (n=10)
$3+\frac{1}{7+\frac{10}{4\cdot5\cdot8-\frac{2}{6\cdot9}}} \approx\pi -2.33\text{e-}08$
see 3+1/(7+10/((4*5*8)-2/(6*9)))
on WolframAlpha
optimal: value error
3+1/(7+10/((4*5*8)-2/(6*9))) 95828/30503 2.33e-08
((1/((10/((4*(5*8))-(2/(6*9))))+7))+3) err=2.33567e-08 95828/30503
(4-(6/(7-(1/(9*((2/5)+((3/8)+10))))))) err=5.96312e-08 85178/27113
((((4/((2*5)+(1/(6*10))))+(7/8))/9)+3) err=6.22542e-08 135943/43272
((1/((5/(((4+6)*8)-((2/9)/10)))+7))+3) err=8.13969e-08 79853/25418
(((1-(4/(9*(5*((2/(6*8))+10)))))/7)+3) err=8.29516e-08 79498/25305
((1/((2/((4*8)-(5/(6*(9*10)))))+7))+3) err=9.59077e-08 76658/24401
Smart Search (n=11) (nearly exhaustive?)
$\frac{11}{4}+\frac{2}{5+\frac{6+\frac{1}{9\cdot10-3}}{7\cdot8}} \approx\pi +2.91\text{e-}11$
((2/((((6+(1/((9*10)-3)))/8)/7)+5))+(11/4)) err=2.91434e-11 312689/99532
((10/(((9-((2/(7+((5/11)/4)))/6))*8)-1))+3) err=1.22356e-10 208341/66317
((8/((1/(((4*(5*6))-(3/(10*11)))+9))+7))+2) err=2.74029e-10 312334/99419
(((1/(2+5))-(6/((8*(9*((10-4)*11)))-7)))+3) err=3.31628e-10 104348/33215
(((1-((10/(7+(4/(11-(5/8)))))/9))/6)+3) err=5.77891e-10 103993/33102
Smart Search (n=12) (nearly exhaustive?)
$3+\frac{1}{7+\frac{2}{4\cdot8-\frac{11}{9\cdot10(6+12)-5}}} \approx\pi +1.61\text{e-}12$
((1/((2/((4*8)-(11/((9*(10*(6+12)))-5))))+7))+3) err=1.61071e-12 1146408/364913
((1/(((5/(8-(2/(9*((11*12)-(6/4))))))/10)+7))+3) err=8.71525e-12 833719/265381
(6/(((2+4)/((3/(10+(1/(8*(11*12)))))+5))+(7/9))) err=1.8701e-11 3022542/962105
((((8/((((9+(2/(6+(10*11))))/12)/7)+5))-1)/4)+3) err=2.91434e-11 312689/99532
((1/((2/((4*8)-(9/((6/5)+(10*(11*12))))))+7))+3) err=3.14357e-11 521030/165849
((2/((5+10)-((7-(1/(9*((4*(11*12))-6))))/8)))+3) err=4.80691e-11 1667793/530875
((12/((7/(10-(2/((1/(4*5))+6))))+3))-(8/(9*11))) err=5.24358e-11 1355104/431343
((1/(((2/(8-(10/(11*((5*(9*12))-6)))))/4)+7))+3) err=5.94227e-11 1042415/331811
((1/((2/((4*8)-(9/((6+(10*(11*12)))-5))))+7))+3) err=7.18372e-11 937712/298483
(((5/(7-(11/((4*10)-(3/8)))))-(2/(9+(1/12))))*6) err=7.23981e-11 729726/232279
((2-((11/((4/(7*9))+12))/10))*((5/3)-(1/(6*8)))) err=8.1021e-11 1146053/364800
((3/(8/9))-(7/((6-(1/(((4*11)-(2/10))*12)))*5))) err=9.28817e-11 1980837/630520
Smart Search (n=13) (70%?? exhaustive)
$3+\frac{5}{(6+11)2}-\frac{4}{(\frac{1}{7}+8)9\cdot10-\frac{13}{12}} \approx\pi +2.99\text{e-}13$
((((5/(6+11))/2)-(4/((((1/7)+8)*(9*10))-(13/12))))+3) err=2.9976e-13 6565759/2089946
(((13-(1/(10*((7*12)-(5/11)))))/4)-(8/(2+(6*(3+9))))) err=4.04121e-13 4272943/1360120
((1/((((((9-2)/(12*((11*13)-6)))/4)+5)/(8*10))+7))+3) err=6.01741e-13 11672421/3715447
(((2/(((11/5)+12)*((1/10)+13)))+(7/((6*9)-(4/8))))+3) err=1.14264e-12 3126535/995207
((1/((5/(((13-((11/(9+(8*(10*12))))/4))*6)+2))+7))+3) err=1.61071e-12 1146408/364913
(4-(6/(7-((11/(12-((3/(5+(8*13)))/2)))/((9*10)-1))))) err=1.76081e-12 5106662/1625501
((((9/((10+(2/(8-(((7/12)/6)/4))))+(5/11)))+1)/13)+3) err=2.28573e-12 11047043/3516383
((1/(((((5/(6+(11*((9*(10*12))-13))))+2)/4)/8)+7))+3) err=2.64322e-12 8337545/2653923
(((1-((4/(5-((12-(13/(11-(2/(8*10)))))/9)))/7))/6)+3) err=2.73692e-12 1980127/630294
((((((2/((9/8)+((7/(10*13))/5)))+1)/12)+6)/(4*11))+3) err=3.36842e-12 4898321/1559184
((1/((2/((4*8)-(5/(9+(6*((10*12)+(11/13)))))))+7))+3) err=3.47278e-12 6774100/2156263
((1/(((((9/(8-(4/((6*(11*13))-12))))+2)/5)/10)+7))+3) err=3.90532e-12 3751913/1194271
((1/((2/((4*8)-(9/((10*(11*12))+((13-5)/6)))))+7))+3) err=4.50839e-12 2813846/895675
(7/((2-(1/(5*((3*6)+(10+(11/(12*13)))))))+(4/(8+9)))) err=4.91474e-12 2605505/829358
((8/((1/(11*((7*(12*13))-(2/9))))+3))+((6-(5/4))/10)) err=4.93872e-12 40748593/12970680
note: my code prints the error out as 2.9976e-13 instead of 2.995199e-13 because double-precision math is accurate to only ~16 digits.
Smart Search (n=14) (and k=8)
$3+\frac{2}{14+\frac{1}{8-\frac{9}{11(4(10\cdot12)+\frac{7}{13+\frac{6}{5}})}}}\approx\pi-5.20\text{e-}15$
((2/((1/(8-(9/(11*((4*(10*12))+(7/((6/5)+13)))))))+14))+3) err=4.88498e-15 133190959/42395999
((((2/(((9-(6/((8+11)*13)))*14)-(1/12)))+(7/5))/10)+3) err=8.88178e-15 58466453/18610450
(2/((((3/(5*((9*((8*12)-14))-(1/11))))+(7/4))/10)+(6/13))) err=2.08722e-14 42208400/13435351
((10+((3+13)/(6+((9/(5+14))/8))))/(4+(2/(7*((1/11)+12))))) err=2.17604e-14 5419351/1725033
((10/3)-(11/(((7+((6+(1/13))/((5/9)+(2*14))))*8)-(4/12)))) err=2.22045e-14 5419351/1725033
((1/(((2/(4-(13/(((11+(9*(10*12)))*14)-5))))/8)+7))+3) err=2.22045e-14 5419351/1725033
((2/((((7/((4*(6*(10*(5+(11*12)))))+(1/14)))+9)/8)+13))+3) err=2.22045e-14 163414249/52016371
((((7/((10*(8-(1/11)))+(((13/14)/12)/4)))+6)/((5*9)-2))+3) err=2.39808e-14 78997449/25145669
((8/(((1/(10-(((3/(4*6))+12)/((11*14)-(5/9)))))/13)+7))+2) err=3.55271e-14 31369698/9985285
((2/(((((6/(11*(((4*10)-(7/12))*(14-1))))/5)+9)/8)+13))+3) err=3.81917e-14 120059441/38216107
((2/((1/(8-(10/((6+(9*((4+((7/11)/5))*12)))*13))))+14))+3) err=4.13003e-14 57320045/18245537
((6/(11*(12+(5/((10*(9+(8*14)))-7)))))+(3+((1/4)-(2/13)))) err=4.79616e-14 25950347/8260252
(((1-((5/((8*(6+(12/(13+(9/(10*(2+14)))))))-4))/11))/7)+3) err=4.79616e-14 25950347/8260252
(((9-(((5-(1/(10*(12*((4/7)+14)))))/8)/(6+11)))/3)+(2/13)) err=4.88498e-14 203955211/64920960
((1/((6/((8*12)-((9/(10*(11+(2/((13*14)-5)))))/4)))+7))+3) err=5.50671e-14 55339918/17615243
(4-(5/(6-((14/8)/(10-(2/(3+(11*(12+(1/((7+9)*13))))))))))) err=6.66134e-14 20530996/6535219
((2/((5/((4*10)-(12/((((6/7)+9)*(11*13))-(1/8)))))+14))+3) err=7.41629e-14 140069407/44585477
((2/((9/(8-(1/(12*((4*(10*11))+(7/(5+14)))))))+13))+3) err=7.99361e-14 35642641/11345405
((1/((5/((8*10)-((9/((12-2)*(6+14)))-(4/(11*13)))))+7))+3) err=8.52651e-14 50754286/16155591
((10/(((1-((6/((8*12)+(4/(9*13))))/5))/14)+7))+(2-(3/11))) err=9.14824e-14 96089221/30586149
((((2/((1/(10*(12-(11/((6*(13*14))-4)))))+5))+(7/8))/9)+3) err=9.63674e-14 73890787/23520168
((1/(8-(((2/11)+12)/(13-(4/((5/7)+(10*((6*9)+14))))))))+3) err=9.81437e-14 15111645/4810186
note: more rounding errors, and now duplicated fractions
(n=15)
$3+\frac{1}{2+15}+\frac{\frac{12}{7+\frac{10}{6\cdot8(14-\frac{9}{13})}}-\frac{4}{5}}{11}\approx\pi+8.60\text{e-}16$
3+((((12/(7+(((10/(14-(9/13)))/8)/6)))-(4/5))/11)+(1/(2+15))) = 85563208/27235615
3+(2/((9/(8-((7/(((5+10)*(14*15))-(11/6)))/(12-(1/4)))))+13)) err= 9.6984e-16 14204192/100317295
How
Exhaustive search
Let $F(S)$ be the set of numbers you can "achieve" using the numbers in set $S$.
For example,
$F(\{3\}) = \{3\}$
$F(\{3,4\}) = \{3,4,7,-1,1,12,\frac{3}{4},\frac{4}{3}\}$
Then the problem is to find the element in $F(\{1,2,3,...,n\})$ nearest $\pi$.
How can you calculate $F(S)$? Let's consider this element of $F(\{1,2,3,4\})$:
$$
\frac{1}{3}+4\cdot2
$$
The outer-most operation is addition. So it's an element of $F(\{1,3\})$ $+$ an element of $F(\{2,4\})$. Generalizing this gives you a way to compute $F(\{1,2,...,n\})$. Note that this involves computing $F$ for $2^{n}-1$ subsets.
Smart search
Consider the element in $F(\{1,2,...,10\})$ nearest $\pi$, (where $\epsilon$ is about $-2.33e-08$):
$$
\pi +\epsilon =3+\frac{1}{7+\frac{10}{4\cdot5\cdot8-\frac{2}{6\cdot9}}}
$$
Let's move some of the numbers to the left side of the equation:
$$
\frac{10}{\frac{1}{(\pi +\epsilon)-3}-7} =4\cdot5\cdot8-\frac{2}{6\cdot9}
$$
Hmm, so this version could have been discovered by calculating $F(\{\pi,1,3,7,10\})$ and $F(\{2,4,5,6,8,9\})$ and considering pairs of elements that are nearly equal (and then solving for $\epsilon$).
Better yet, for each element of $F(\{\pi,1,3,7,10\})$, replace $\pi$ with $\pi+0.00001$ and then $\pi-0.00001$ to get a range of values. For example,
$$
\frac{10}{\frac{1}{(\pi \pm 0.00001)-3}-7}
$$
gives the range $[158.699,161.252]$ and $4\cdot5\cdot8-\frac{2}{6\cdot9}$ is within this range. So, solving for $\pi$ guarantees an error less than $0.00001$.
Generalizing this observation gives the "Smart Search". Split $\{\pi,1,2,...,n\}$ into two pieces, where the side without $\pi$ has exactly $k$ elements (it's best for $k$ to be near $n/2$). In the example above $k$ was $6$. Notice that $k=7$ would uncover the same result, but $k=5$ would miss it, because $4\cdot5\cdot8$ and $\frac{2}{6\cdot9}$ use three numbers each.
Anyways, this technique allows my computer to search up to $n=14$ with $k=8$, instead of the exhaustive search which uses too much RAM at $n=11$ (and is much slower).