It might be possible but you'd need two complete setups. One computer would not be able to run two of the headsets. So you need two hefty gaming computers to make it work. Plus whatever network bandwidth was needed to play two multiplayer games at the same time on your home network.
In a nutshell, unless you have some amazing computers and a state of the art network, you'd probably spend more time trying to make it work than you kids would playing.
I hope this helps.