I have been trying to do what you I think you want done, if you mean that you want to change the color of the picture inside the frame, and then change the color of the frame itself separately. If this is what you mean, I was able to do it like this..
Select the picture inside the frame, save the selection and name it ("inner frame" or something)
Click on quick mask tool, which should turn the picture inside the frame red.
Click on "add to selection " and select around the outside of the frame.
Add an adjustment layer and change the hue-saturation of the frame, or whatever it is you want to do with it.
Click on the quick mask tool again to turn it off.
Now deselect all.
Ok, now the frame should be the color or whatever that you want.
Then go to selection-"read in selection" (or whatever it´s called in English, I mean use the selection of the "inner frame" that you saved earlier.)
Add another adjustment layer, and change the color of the picture, or whatever it was you wanted to do with it.
That was the only way I could figure out to do it, for some reason it didn´t work if I tried changing the picture first, I had to start with the frame. I hope this might at least help a little. 
