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I'm looking to start a small squad of Night Lord's post heresy. I was going to paint them all Necron Abyss, then follow that up with a highlight of Macragge Blue. However Macragge Blue is a base paint (higher pigment content). Could I still highlight with a base paint?

You should be fine using it as a I don't think the higher pigment content makes that much of a difference.

you absolutely can. dont pay too much attention to the base/layer thing.

if you want it to be more transparent to build highlights simply thin it out more.