I need orange eyes for this guy:
I'm using CS2 so I don't know if CS3 has something better.
I would draw around each eye with the pen tool, creating a shape layer. Colour the shape with the orange you choose. (preferably a radial gradient with white in the middle-if you can do that in photoshop?).
Turn down the opacity on each orange eye until it looks realistic. Then use outer glow layer effects on each shape until you reach a desired look. (make sure you use the same properties on each eye to maintain continuity)
I've never actually done this particular effect before but that's how I would start it.
You need to use the selection tool and select the eyes. You may want to copy and paste it so it's on a new layer, or save your selection. Then there are a number of ways to color. You could go to Image> Adjustments> Variations and fool around with that, or use anything else in Adjustments that might be helpful, like Hue/Saturation, or you could just use the paint brush, lower the opacity on it and paint it orange.