I'm using Flash for this because it's well designed for my needs and I can make assets way faster than any other program. Plus it's vector, which is good if you need to export for a game that requires certain resolutions. Also using a Wacom Intuos 5, if you don't have one, I highly suggest it but these assets you can simply make with pencil/paper and a mouse.
To Begin...Start off with a sketch of your character, either directly in your program or by hand and scan it in. Make it simple. I sketch one basic sketch in light color and then make a more detailed sketch above that layer in a darker color.
|We'll call him Paul.|