I'd also suggest to start off dolling in MS Paint, cuz it's the more simpler art programme to use and if you use photoshop etc, you might be tempted to take the lazy person's way out, ie toolshading, in leu of pixel shading. You can always tell when a person's done this, cuz it looks burned and smudgy. O.o
Save dolls in .png to avoid the dreaded gif monster from discolouring your doll's hair and clothes after; you can always turn them into gif later with iaza.
I'd agree with Hayley as far as the doll goes; it's certainly better than my first try. XD Watermelon Bubblegum has a great first doller's tut, and also loads of bases. I'd also recommend If Looks Could Kill... t e m p
for some good, simple bases that are great to doll on. ^^