Simple check for this:
Get a jack cord. One jack into your amp, the other into your new socket.
Touch each of the unknown terminals with a finger, or (e.g.) small screwdriver held by the metal if access is tight.
The one that buzzes is the hot connection to the guitar's circuit, and the earth one you already know.
Don't worry about the unused one, just leave it alone. Don't connect it. If it does get connected to the hot, all your signal will almost certainly stop, since that terminal will be connected to ground once a mono jack is inserted.
You can't be electrocuted by fiddling with a guitar's circuit (I suspect you know this....)
But amps, of course, are different
Never have young children around when working on an amp; they will learn the language you use when you touch live bits, and and this will cause you embarrassment later.
PS I had been unsure of where I first heard that; it was Randall Aiken, I'm now fairly certain.