I used a computer to check all the possibilities. It turns out there are $64$ possible choices of three denominations which allow $18$ distinct values from $30$ to $100$ to be made using three coins. There is no choice that can make $19$ different values that all fall in that range.
15,31,33 15,32,33
16,30,33 16,31,33
17,30,31 17,31,32 17,30,33 17,31,33
18,30,31 18,31,32 18,30,32 18,31,33 18,32,33
19,30,31 19,31,32 19,30,32 19,30,33 19,31,33 19,32,33
20,31,32 20,31,33 20,32,33
21,30,31 21,30,32 21,31,33 21,32,33
22,30,31 22,30,32 22,31,32
23,30,31 23,30,32 23,31,32 23,30,33 23,31,33 23,32,33
24,30,31 24,30,32 24,31,32 24,31,33 24,32,33
25,30,31 25,30,32 25,31,32 25,30,33 25,31,33 25,32,33
26,30,31 26,31,32 26,30,33 26,31,33 26,32,33
27,30,31 27,30,32 27,31,32 27,32,33
28,31,32 28,30,33 28,31,33 28,32,33
29,30,33 29,32,33
30,31,33 30,32,33 30,31,34
Now the second question.
Since $k=5$ coins can make at most $56$ distinct values (or $55$ if we discount the value of $0$), we need at least $6$ coins. Again I used a computer for this, and it turns out that