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Im currently using mechrite red as a base and scorched brown for shoulderguards with black trim. Weapons and crests are chainmail, tin bits, and burnished gold (not really fond of this gold though). The only GW products retail inside a 6 hour drive (that I only recently discovered) is still 1.5 hours away so I'd like to make my trips count. I'd like to start practicing with highlights, shading and washes but I'm not sure what washes or layers to use for highlights. Also with that color scheme I cant decide which color to use with the red on vehicles.

If someone with more color experience could offer some insight or point me in the direction of a good guide for color selection that would awesome. =D

Get a colour wheel. Absolutely useful.