In the moon image you can see, that the artist was using a backlit style,which is typicall for a cinematic lighting.The hair the finger and the logo are toplit.And the eyes left white completly to get a face expression and not get a complete dark face.
You should try to analize the light in your comic scenes and why they are lit how its lit.
For the backlit shaderstyle you could use a simple layerweight node maybe multiplyed with lightpath is shadow as factor between the colors and darken color before it goes into the shader.
something like this
Your 2nd render looks not that bad.I think you can optimize the contrast between color and shadow even more with gamma or colorramp as fac.You should give the hair a different shading/lighting.
about the model.At the hands it seems that some normals are flipped or mesh is not closed or something.You can give a try to recalc the normal direction to the outside.