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Here is where I start the real fun; My image has already been flatted using assorted brushes and I'm ready to stary laying down assorted tones to flesh out the figure. For most of this piece I used larger brushes on a lower opacity, around 40-70% hardness. So all the brushes have an edge, but it's soft.
I decide to start with her cape, and select parts of it with the lasso tool, then hide the selection so I don't have to watch the crawling ants while I work. (CTRL+H) For whatever reason, I designed this character with a split cape, which lends to a more interesting look. Using a large, light brush I lay on some basic shades to give me a an idea of where shadows will fall in the assorted folds.
Don't forget about cast shadows from one object to another. In this case, a cast shadow from her arm onto the cape.
I add in darker shadows using a brush on Multiply.
Then went back and added in some highlights. I use both brushes on Normal and on Screen for the assorted highlights.

Next I move onto her pants. First I shade out the basic areas of shadow to define the shape of her legs. Remember the cast shadow from the wand.
Then I go back with a smaller brush and add in wrinkles in the pants. I use both dark and light brushes to define the wrinkles and folds.
I then use large, very soft brushes to add in broad highlighst and very subtle shadows to better round out her legs.

Same as with the pants, I start the gloves with a basic definition of shadows.
Then I go back and refine wrinkles, and add some darker shadows.
I refine shadows again, then add in highlights. Notice how the arm on the left has more shadows than the other. Because it's behind her body, while the other is more in the light, the two arms are receiving different amount of light, and thus their values are different when I render them.