Well...
I always use Photoshop whenever i wanna paint something.
But im not sure what you mean by character?
I some times just use freehand & then scan my picture in black & white with fairly high resolution & then i just load it up into Photoshop & edit the colors.
You see, there`s a really great option in Photoshop called "Layers", with this option you can basicly puth any colors behind the picture.... um?.....
Im not sure i made myself clear on that....anyway.
Whenever i start to paint a new skin...i never know what it will look like in the end.
I always have an idea...but it always turn out be something more or less crappy.
Im just lucky.
(Who needs talent? All you need is a open mind.)
It can be hard to paint freehand using only your mouse.....it takes practice i guess.
No biggy, anyone can paint.
My best solution to your little problem would be to paint whatever you want on paper (black n white) & then add color to it in Photoshop.
.: Masamune :.