Do NOT paint the eyes white and then try to paint the iris. It'll look bug-eyed. It really makes my skin crawl when I see people do a gorgeous paint job and then frak it up with the 80's noob-style Marty Feldman eyes.
I used to know a guy who bragged about pulling out his own hairs to paint the irises on his figs. I pointed out it still looked crappy. He retorted with something to the effect of "well you don't even paint yours!"
Well, I do to. I either paint them black and/or I just double up on the wash in that area. I only ever bother any "eyes" on special models.
Why? I'm glad you asked. A great man named George Washington once said "Don't shoot till you see the whites of their eyes!" Ok, so if that figure was a real guy as far away as the mini is small, you wouldn't be able to see the whites of his eyes. You wouldn't even be able to tell what color his irises were.
But if you must....then follow Curnow's advice after the wash step. You can paint around finished eyes, but it's really hard not to get your wash in them...assuming you use that technique on faces.
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