Here is a screenie of my *recent* workflow, one that I like a lot. I try to keep it simple, as few layers as possible (the sketch one isn't really used), a limited palette (that I do modify a little) and only 3 brushes. I start off with a big block brush, getting the shape down, then go in with a pencil to define some things. Then I hit it with a block brush on the "paint" layer, followed by the "graphite shadow" brush on the "texture" layer (which upon further inspection doesn't exist! What the hell file did I start from? It's of course above paint yet below line. I am officially banned from software tutorials), then black pencil to define and color again to accent things; then back and forth like this maddeningly until something happens. The brush window shown isn't even used, but it rounded off the screencap nicely :) Also, sometimes I sketch preliminary ideas on paper, sometimes blocking in provides enough form to work from.
Edit: looks like blocking and paint are out of order! You guys get the hint. Also, I will probably delete the sketch layer. This is saved as a "default_char" file, so that all the layers are set up and ready to go for any new design.
Edit2: I can't stop. I use a USB numpad, that was like 10 bucks, that I map brush opacity/size, eraser, color picker, etc. to. This makes it nice when using a tablet- right hand on the pen, left doing the rest of brush control. GANGBUSTERS!
