Basically, find the color of the background and subtract it, but I guess you knew this. It's a little tricky to do this all automatically, but it seems possible.
First, take a look at blob detection with OpenCV and see if this is basically done for you.
To do it yourself:
find the background: There are several options. Probably easiest is to histogram the image, and the large number of pixels with similar values are the background, and if there are two large collections, the background will be the one with a big hole in the middle. Another approach is to take a band around the perimeter as the background color, but this seems inferior as, for example, reflection from a flash could dramatically brighten more centrally located background pixels.
remove the background: a first take at this would be to threshold the image based on the background color, and then run the "open" or "close" algorithms on this, and then use this as a mask to select your clothing article. (The point of open/close is to not remove small background colored items on the clothing, like black buttons on a white blouse, or, say, bright reflections on black clothing.)
OpenCV is a good tool for this.
The trickiest part of this will probably be at the shadow around the object (e.g. a black jacket on a white background will have a continuous gray shadow at some of the edges and where to make this cut?), but if you get this far, post another question.