@JR > Yes I believe you should be able to do this, but it will take away from other controls as you will have to re-map some of your buttons.
My suggestion would be to re-map the "Hot Cue" buttons if you do not use them much, and set them to play the current decks samples. So you will still have to switch decks in order to use them. I don't think you could program them to work universally across 2 decks at a time.