Upon reaching Level 10, a Town unlocks the Ambassador Citizen. The Ambassador is where all diplomatic treaties are crafted, reviewed, and received - so this Citizen will be your lifeline to Diplomacy. (It's important to note that if your Nation trades away its last Level 10 or higher Town, you won't be able to take part in Diplomacy until you once again control a Town with an Ambassador.)
To get started, simply speak with your Ambassador and go to the Manage Diplomatic Relations menu. From there, you'll be able to access the following: