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That is, "To make your painting more lively, if your shading is has a cool tone, than your highlight must be warm toned, and vice versa". What you have there is a rather cold shade of purple for a shadow, and then a warm, energetic light purple highlight - and as you said, more red tinted.
In a lot of great paintings, if not all, you will see the rule applied. I can't really guess whether you knew of this rule or not, but either way, you were definitely on the ball with that one!
I haven't tried this personally, but wanna see what happens if you put a secondary outline (for a lack of a better term) around your sprites? Something like... this example you conveniently put in your own profile page: [link]
Better yet, have you tried putting an outline at all?