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Looks like putting on make-up, but no no- it's much more effective!
Sorry PSP users- this tutorial involves selective coloring (this works on 'normal' images too, not just eye close ups)
1. Selective coloring layer;
Reds: -100, 0, +100, 0
Yellows: -100, +16, +21, +11
Neutrals: +23, +2, -18, +3.
2. Delete everything on the selective coloring layer around the eye (otherwise it's too orange-ish, so it doesn't really look that real).
3. Flatten your image, duplicate your new base, set that layer to soft light at low opacity (20-30%).
Done!