Out of the box, no. But with such a cool case, and some effort, everything is possible!
The best approach would depend on the hardware you find inside.
If you could 'read' the state of each of the seven buttons, you can use the GPIO pins to read out the current state, and hook up a script to act on that.
Depending on your coding skills, you could brew up your own EmulationStation to accept specific system.cfg files, depending on what button is pressed, and killing it when a state-change is detected.
On the other hand, it might be much easier to forego the latching buttons, and replace them with momentary pushbuttons. You will loose some retro-style points, but there will be much less work to do on the coding front.