I have trouble with colour.

The logical part of my brain says "this thing is this colour, so draw it that colour." The creative part of my brain says "Colour theory! Let's try using purple and orange!". My brain then shuts down and can't decide between the two - boring but accurate to character or exciting but you can't tell what colour it was supposed to be in the first place...

I literally have no idea how people manage to do such amazing drawings of characters that have cool colour work that's still recognisable as the "right" colouring. Is there some magic trick I'm missing? I really want to improve but I've got no idea where to go. Anyone able to shed some light? I'd love to learn a thing or two - perhaps some exercises or a good site?