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I read this article, and a TL;DR of it is that the guy primes a model black, the sprays a quick white from above, which gives a pretty cool effect together with some shades and highlights:



Any tips on how to do this? I feel like spraying a coat of white on top of black is wrong...

Also, would I get a similar effect if instead of black the armour was painted in a dark grey?

Yep. The only thing with using a 2 (or 3) can method rather than multiple mixes with an airbrush is you get a very 'spotty' colour transition. Since you're using these coats as a guide for highlights and shade it's normally not that noticeable once you've got lots of layers on. Typically you use this to place shade and highlight blocks, then paint a block of the midtone and blend that into your highlights. It's a good way of working.