This painting was time-consuming and a lot of hard work. I made sure to save every step so you can all share the pain I went through. Muwahahaha!
I start with a sketch(Photoshop--no particular reason. I can draw in both Photoshop and Painter).
I lay down some basic colors. The drawing is kept on a Multiply layer in Photoshop.
I block in the shadows in another Multiply layer, trying to capture the general lighting and feel for the piece. (Up to this point, it's all Photoshop.)