Yeah it does sound cool. I've looked at several toys done in the paint and my only concern would be the colors. Every thing I've seen has that "shiny candy" look. I think though that most of the artists using V-Color use the gloss clear coat over their paint work, because that's the effect they're going for.
The paint can be applied with a bristle brush. Here is a link to a forum conversation about "where for's and how too's" of the product....
http://skullbrain.org/bb/viewtopic.php?f=19&t=17489 Some very interesting stuff with-in that thread. I found it last night.
Upon digging last night for info on the V-Color paint I came across something even more interesting, Monster Color. Here's a link:
http://www.monsterkolorstore.com/This stuff looks even better than the V-Color to me. Again some of the colors are too bright for what we do here, but there are some of the very basic colors and they can probably be toned down with a wash over. They are brush able and would probably solve the problem of joint wear that occurs with acrylics. There are also Monster Color Markers for finer detail.

These may be worth a try alone. They also sell resin dyes for use with Smooth-On Resins!
Check out this video for the paint:
http://www.youtube.com/watch?v=ep4HWFcsEakWhen I found the Monster Color video I also found this very helpful video on painting eyes. Very much worth a look...
http://www.youtube.com/watch?v=GIzxQP2XxlYI really hope this is helpful to some of you out there.