It's not that difficult conceptually, and will make How It All Works much clearer than any other thing you can do. After all, once you get the connection made and can pass text back and forth, creating a service is just all about how it's processed at each end.
To my mind, I'd start with the socket basics, keep it quite basic, and point them at further info if they wish to follow up on their own. After seeing how sockets work, showing them the kinds of things you can do with nmap etc will be much much clearer to them. Start down near the root, and move the course further up the tree as it progresses.