/3/ - 3DCG

>>579634
once you get the general color ramp set up you should be able to see how the geometry affects the shading so you can sculpt / tweak the surface to create the smoothed, almost chubby, features and that eye hook shape.

i think you should also have a rim light made from a negative dot normal masked to appear stronger in shadow / where inverted normals are lit and faintly elsewhere but then you get into nodes and not a quick material.

http://www.valvesoftware.com/publications/2007/NPAR07_IllustrativeRenderingInTeamFortress2.pdf
http://www.valvesoftware.com/publications/2007/NPAR07_IllustrativeRenderingInTeamFortress2_Slides.pdf

tf2 is also based on a 50s illustration aesthetic, you might find some useful information or inspiration in valve's writeups on the process.