Hey Rufus,
Ok.. here's what I did (using Corel Photo-Paint this time, but the steps are the same as Photoshop).
Firstly, mask off the area you want:
Then, you can either paint using the colour replacement tool as you did earlier, or else for the case of wanting black or grey, you can "desaturate" the selection in one hit with the appropriate menu item.
That pretty much gets you where you were before, with a grey car. Now we need to edit the Curve of the selection to make the grey appear black. Instead of simply darkening the whole image, I try to retain the highlights so that specular highlights and bright reflections on the car will remain. Just as long as you bring that middle grey down a lot, it will start to look black. Below is the curve I used in this case, but it will probably vary from image to image - just fiddle until it looks OK.
And here is the finished product.... well.. at least the main part of the body looks kind of black. You can see that the front bumper (which was coming from a red, not a black) would need a march darker curve to make it look black.
Incidently, when you are using the "colour replacement" tool... It only replaces the Hue and Saturation of the image you swipe it over, it doesn't alter the luminescence (or lightness or "value") of the pixels. So it wouldn't matter if you went over it in white, grey, or black... as all these "colours" have no hue or saturation so the end result is the same. Try using the colour replacement tool with a dark red, and then with a light red of exactly the same hue and saturation. I think you'll find the end results come out identical as well.
Oh, and as for the photo of you with the alien eyes... well, instead of trying to darken them I thought "why fight it?" and went with the flow instead:
Edit: awww... after hitting "submit" I noticed that in the time I wrote this, Slej posted a much better picture with cloned eyes.... rats! good one slej! classic!
Seriously, I think green-eye reflections like those are beyond repair with a simple colour-replacing (and I did try, but nothing gave satisfactory results).
What I would suggest is taking some nice front-on photos of your (dogs) eyes in normal daylight with nicely diffused lighting. Maybe take a few from different angles, with different lighting. Then keep all these images stored away somewhere for later.
Then, whenever you take a photo suffering from green-eye like this, simply open the image with your "good eyes" in it and use the clone-brush to paint over the green with what the eyes look like in normal light. I think you'll end up with much better results.
Hope that helps!
Cheers
Adrian