Agreed. Any method you choose for masking / selecting background area will be imperfect for portraiture as hair is always difficult and even the relatively 'clean' boundaries between skin and background are very hard to get looking natural.
Use a white background in the first place, doesn't have to be perfect. Light it separately if you can, at least 2 stops brighter than your main exposure - more if your white background isn't as white as you'd like it! If you want to render the background as pure white in PS, use levels and / or curves, masked if necessary.