Colour using layers organised like this:
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Use silhouettes to get your mind thinking in a way that strengthens your characters. When posing a character, it’s a good idea to act them out, in your head or physically. Take reference photos; posing helps you understand the stance and personality better. You can always pose a sketching Doll, or a Biped in 3ds Max, to get a better idea of shape and action lines too.
Gather a selection of images from a range of artists, depict an assortment of styles in keeping with your art direction. Eventually, you’ll want to start narrowing them down and categorising.