If you can't do it in Premiere Pro you can try your hand at the RotoBrush tool in After Effects CS6 and later.
I was recently doing some VFX for a movie shot in the snow, so a lot of the time I was cutting people out from white backgrounds. I found in many cases that a luma key would do most of the hard work for me.
The simple answer is yes. If it is reasonably clean and if there isn't any white in the person or thing being keyed out.
If there is some white in the person or object, use a garbage matte to hide the white in the person so the key does not work in that area.If the white is too close to the edges, see post #1