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Realistically, you can't see much of a person's eyes when they're as small as a 40K model. You can just paint them black, and that looks fine.

However, people like to be able to see the whites. This can be tricky to do without making the model look surprised, but if you do it right, you can add some personality, convey that he's looking in a given direction, etc.

The way I do an eye with whites is to fill it in black, roughly an oval shape, then put a white dot on either side of the oval. Use a small brush, or even the tip of a sharp object like a toothpick or knife, so the dot is very, very small.

Sometimes you overdo the white, then just clean up with more black. You may find it easier to go black, white inner, black over that for the pupil.

Just practice from there.