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Anything I need to bare in mind? I assume with layer paints I would have to add a bit more to get a true 1:1 mix with the base paint due to less pigment, is that right?

not necessarily. It's best to work your way to the color you want rather than going straight for it unless you already know the mix ratios.

Pigment opacity and value varies through the line, base or layer. Some layers cover well, some bases are mediocre.

I really don't see the 2 as seperate when I'm mixing paints. I don't usually even think about it. I've had base paints that have had less opacity than layer. (looking at you lupercal green) just mix em, there's nothing else to it.

Yeah you can just mix them and there are no issues, at least in my case I've come across none.