This is a study I did trying out two different approaches:
A (my usual workflow)
1. Starting with a color base, separated in layers. Before I start adding values I use the selection tool and save different selections, to use while rendering.
2. Building the shadows on top, on a fill layer set to multiply (and paint on the mask)
3. Build the lights on a fill layer (color of choice for the light) and paint in the mask
4. Add a layer set to overlay, paint to adjust colours. If necessary also a layer set to normal and do a paint over.
Option B is just take the same color base, merge the layers and start painting, using the same selections.