In the previous version for Outlook for mac, in order to create a new identity, or profile, you would open up the Database Utility to create the new identity. This has changed for Office for Mac 2016, identities are now referred to as profiles, and the Database Utility is now called "Outlook Profile Manager".
Creating a new Profile.
Open up the Finder app, and browse to the Application folder, and locate Microsoft Outlook.
Press and hold the CTRL key and click the Microsoft Outlook Icon to bring up the contextual menu, and Select Show Package Contents.
Click on the Contents folder.
Click on the SharedSupport folder.
Once in the SharedSupport folder, double-click Outlook Profile Manager.
In the Outlook Profile Manager window, click the Add (+) button and give the profile a name, then select the gear icon and select Set as Default. You can now close out of the Outlook Profile manager and re configure your email account within Outlook.