Depends what you're doing.
For eyes, you can usually put little points of white, which are small enough that they're just white, and don't need coats.
For skulls, you generally want to layer them in the frst place, so you're just doing what you would normally do. Basecoat some sort of mid brown or tan, layer on something lighter, then white for the final highlights.
Although with skulls, going all the way to white is usually a bit bright and chalky looking. Usually the highlights want to be a few steps shy of white.
I don't have a ton of experience with them yet, but the Foundation paints GW is putting out seem to be very good for basecoats of this sort.
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