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Its not really possible to give detailed steps based on your description, there are a several considerations and its hard to say the best process without seeing the photo. Some of the factors would be, how drastic of a change you wanted to make, whether the changes you wanted to make are only to certain parts of the picture, and if you did want to adjust only certain parts, how easy it is to isolate these parts from the rest of the image. So if the orange glow is something that is throughout the entire picture (like a color cast) you could select the entire the image and make color adjustments, if it was only on the face itself, you would want to only select the areas you wanted to change before making adjustments. There is no set "you have to do it this way", there are probably multiple ways it could be accomplished and the actual process would probably vary from photo to photo. Based on your description, the process that comes to mind for me would be using adjustments from the Adjustments section to move the orange hues into whatever color range you wanted (blues?) to look more neutral, natural, or professional. The Temperature and Color Balance adjustments might be good for this process. It may take a little while to learn how to accomplish what you want with the product if you haven't used other Photoshop products before. I'd definately recommend going through the tutorials if you haven't already, its a great way to learn the way the program works. There may not be a tutorial extactly like what you're wanting to accomplish with the product but once you get a good handle on the way the tools work, you'll find your own creativity and time you want to spend edting are your only limitations.
Hope that helps
Do you think you could post an example of the type of effect you are trying to achieve? Is there an image that inspired you that you could share with this community? There are several experts that read this forum and might have some suggestions.
This is when the art of Photoshop really shines! And no doubt it IS an art.
Since you're using PST, you may want to use the "flashlight trick" (which, incidentally, Adobe has a Russell Brown tutorial video about that is excellent). Its over at <http://tv.adobe.com/show/learn-photoshop-touch/>
This trick basically utilizes the very cool Camera Fill command. I don't want to explain the whole process here (since the video is PERFECT) but this command can fill selections with a "real" photo (taken with the on-board camera)! If you make the orig the bottom layer you can make a new layer for the effect. In a dark room, a flashlight can be used to relight scenes! Amazing.
You will still need to adjust tonal curves (that's the best way w/o cam fill) later down the line most likely but I don't even know if you can in PST.
Seriously, check out the videos--they are really good!