I used a reference photo from a paused frame, and began by doing a rough sketch.
I begin the painting process by blocking in the main skin color
Basic shadows and highlights are defined. I use the burn and dodge tool to roughly establish the light and dark areas. I also add some varying hues to the skin and block in the main hair color
Further defining shadows and highlights. In this picture, there is some heavy backlighting, so the front of the face is quite shaded. I use the burn and dodge tool again with some Paintbrush also to further define these shapes and give volume to the face and armor
A little bit of Levels corrections before using the Paintbrush to smoothen out the colors. I add purples, blues and greens to give life to the skin. I alternate between the Paintbrush and the color picker tool to choose intermediary colors while color blending.
Some final color correction and a little bit of highlights around the edges and I'm done.