The Users page of the Web UI is pretty basic. It has all the standard navigation capabilities of the other list pages like Computers. However this page is simply a list of all the user names that have been reported by the ITAM agent on your endpoints as having logged in to the machine.
Note that if you don't see the Users page in the main navigation, it could be disabled which is the default. Click on your account name in the upper right and Edit Account to enable (or disable) main navigation items.
These records have no relation to Accounts at all. This is simply a database table used to cross reference Usage at the fundamental design level. There are use cases beyond that however, like linking an Owner on an asset, and using various Extras. You can therefore also use a Script to import user meta data from a directory system like Azure.