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I am painting Orks. I got greenskin colored primer from Army Painter. Am I to understand the primer will act as my basecoat as well, so I can just move on to highlights and the other colored areas? Sorry if this is a stupid question.

Yes. But I find it works better as a base coat color than a primer.

Personally I use it just like you said; both primer and base coat. Though, it usually helps to do several layers of wash and drybrushing to give the color some more depth.

I gave it a go. The color is fantastic, but I can't seem to paint over it. Did I overprime it or do you think I held the nozzle too close? It said no more than 20cm, and I tried to follow the YouTube video they posted. The paint doesn't seem to coat it at all. I thought I watered my paint down too much, so I tried it straight out of the pot with the same results. The model looks uber glossy and not rough like I see when I use my GW primer.

Am I just stupid? :p

No, I had that happen to me once. Just hit it with a high grade sand paper or emery board, nothing serious just scuff it a little.

I use it as a primer and a basecoat, but I usually hit the model up with a watered-down coat of the same color to catch any spots I missed when spraying. Their Crystal Blue is aces.

I use them on my guard tanks usually I spray necrotic flesh onto the bare plastic then add masking tape to it for camo. Spray leather Brown then remove the masking tape to show the necrotic flesh underneath. Then full wash and paint as normal. No basecoats needed.