Anime might be one of the most difficult face painting designs you'll ever receive a request for, so it's a good idea to have at least one or two of them ready in your repertoire.
Using a number 4 round, use a white face paint in order to sketch your design out. Use your white paint to block out the whites of the eyes over the lids and up through the eyebrows.
Use a second to lighter color from a skin tone pallet and fill in areas where the light might hit the skin.
Fill in the other areas of the skin with darker and lightest skin tones according to where the light might be hitting. Fill in the shirt with orange. At this point it is helpful for me to think of the whole design as a puzzle.
Add darker orange reds to areas that are in shadow on the top/shirt. Line the whites of the eyes with a strong black. Add eyebrows at the tops of the whites of the eyes and include a black pupil. Use black slashes at top of cheeks.
Outline the dark shade on the shadow part of the nose. Add Lines for lips and chin. Add details to the neck and chest. Outline the shirt.
Outline the entire face with black to create the illusion of the face being drawn.
Add a crazy wig, strike a pose, and be the anime character Goku!