They can't: the VideoCall plugin only works if both users are on the same server.
If the purpose is just video calls, you may want to handle registration your own way out of band, and when one person wants to call the other, you have them connect to the same server first and do the registration via VideoCall instead. As an alternative, you can use SIP as the "glue" instead, using a proxy like Kamailio or OpenSIPS to handle registrations, in which case users can indeed connect wherever they want.
L.