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I'm asking because I painted my Dire Avengers with the traditional blue paint scheme with white helmets.
Usually highlighting means adding and dry-brushing a lighter colour to make it seem there is a light source but how do you highlight on white?
I got told this just the other day for my white marines. When you paint white you actually paint a really light grey. Like get astronimican grey and add a lot of white to it so it looks almost pure white (the grey has a lot of strong pigment in it so it will need a fair bit of white). Then highlight with white.
The grey looks white because when light falls on white it comes out really light grey with the most intense light showing white. Test it yourself with a white shirt
Wash: This landing is gonna get pretty interesting.
Mal: Define "interesting".
Wash: [deadpan] Oh God, oh God, we're all going to die?
So I would bascially highlight with Astronomican Grey with added white and then layer within that with skull white?
I'm not much of a painter, more a gamer to be honest, but from my experience of other peoples armies, it tends to be very very very light greys highlighted white.
My Arena Champions: Kharn'eth The Bloodcleaver and Gorzag Iron Jaw
I'd also like to point out that you can change the tone of your white by undercoating with different shades. For instance, if you want your "gray" to be warmer you can use a slightly reddish tone in your gray. You can make a cooler looking gray by using blue in your gray. What ever you do, just make it a very light gray. You can go darker with a light base but it's harder to go lighter with a dark base. After you work with it for a while, you'll see that this is an advantage as much as it is a drawback.
As has been said, you don't highlight white. Instead, spend extra time on the shading. Minus-T has a great tutorial on white power armour in the tutorials section.
The formula that's been working well for me lately (if I ever drag the freakin' camera out, I can take pictures!) is a somewhat simplified version of that, so I can't take total credit for this :
Basecoat with Space Wolves grey (or the equivalent)
Do a CONTROLLED wash with Shadow Grey (or the equivalent). By "controlled," I mean don't just slather it on. Direct it into the cracks and crevasses. Make sure you thin it down a LOT, and use glazing medium.
Clean up the SW grey where appropriate
Finish with straight white. Cover almost all of the SW grey. Only leave a small amount near the cracks and crevasses.
You can experiment with different wash colors, such as straight grey for a less bluish tint, or for more blue, use ice blue. Also, make sure the basecoat is nice, smooth and even. Ditto for the final white. This means multiple, VERY thin coats. Yes, that's gonna take more time, but white is a tough color to do well. It IS worth it, though. I just got the first white SM helmet right about two weeks ago, after spending MONTHS of trial and error with other models. I did a little dance.
As has been said you want to paint a slight off white (mix a blue/grey into a lot of white as it's quicker than adding white to the darker colour) paint this all over. Work those shadow and highlight up in thinned layers of white. It takes a while but ensuring you thin your white and layer prevents chalky, lumpy finishes.
Here is how it can look....