Answer: The most likely distance is the diameter of the planet, when Romeo and Juliet are antipodal.
Assume WLOG Romeo is on the North Pole. Juliet's position is uniformly random on the sphere.
Lemma 1: For the uniform distribution over the sphere, the marginal distribution over the $z$ coordinate is also uniform.
This is a surprising and non-obvious fact about spheres. It's not true for circles or for higher dimensions.
In other words, if you make a slice of an apple that's a fixed width, you always get the same amount of peel. Slices closer to the poles will have a smaller radius, but the peel will be tilted inwards letting more of it fit, and these two effects exactly compensate.
(In this picture, the slices are different widths, but I hope it gets the idea across.)
Proof
See the calculation from Mathworld for the surface area of a zone.
The surface area is computed to be $2 \pi r h$ (where $r$ is the sphere's radius), which is proportional to the thickness $h$ and independent the position of the slice given by $a$ and $b$.
So, Juliet's position can be randomly generated by picking a uniformly random $z$-coordinate. Therefore, the most likely distance is the one corresponding to the infinitesimal slice $\mathrm{d}z$ that compresses to the smallest range of distances $\left| \mathrm{d}D \right|$, maximizing the probability density. This problem is unchanged if we instead consider points on a two-dimensional circle.
The distance $D$ between Romeo's position $(0, r)$ and Juliet's position $(\sqrt{r^2-z^2},z)$ is given by
$$D^2 = r^2 - z^2 + (z-r)^2 = 2r(r-z)$$
Then, taking the derivative with respect to $z$ gives
$$2 D \thinspace \mathrm{d}D = -2r \thinspace \mathrm{dz}$$
and so the infinitesimal range of distances
$$ \left| \mathrm{d}D \right| = r \thinspace \mathrm{dz} / D $$
This is minimized when $D$ is maximized. So, the most likely distance is the maximum one of the diameter, when Romeo and Juliet are antipodal.
We've also shown that the distribution of distance squared is uniform.