To connect to a remote computer you need to know its address. So when you invite someone, you must start a local server, let TNet open up proper ports via UPnP (which may not be possible 100%!), and send your external and internal IP addresses to the person you're inviting.
The other person will then try to establish a connection with you by using those addresses. Once a connection is made, you can join the same channel and start communicating. Note that the best way to achieve what you're trying to do is to make sure that your game is designed with multiplayer in mind, and it's going to be very difficult to do this without first understanding the basics of TNet and how to sync data. Start with simple things first. Once you understand how data is sent via TNet and how to make it persistent you should have a solid understanding of what's needed to achieve what you want with your game.