Any person wishing to use the Live Assist application must first have a user created for them in Dynamics 365. When starting a Dynamics trial, you will be prompted to add users upon arriving at the Office 365 Admin Center. (You can also add users individually by selecting "Users" > "Add a User".)
Click on "Go to setup" to launch the Dynamics 365 Setup Wizard. The first step of the wizard is where you can add Dynamics users. Enter your desired display names and usernames, and then click "Next".
You will need to communicate these credentials out to your new users. There are a few different ways you can do this: one of them is to have the system email each user at an alternative email address. This can be done using the first tab on the "Share sign-in credentials" screen.
Alternatively, you can use one of the other tabs to either download or print the credentials, and distribute them yourself. The "download" option is depicted below. Click "Next" when you are finished with this step.
The next step ("Add apps") is optional. Click "Next" to bypass this step. (You can always return to the admin center if you wish to add apps later.)
That completes the wizard! Now you can follow steps 3 and 4 in How to create a Live Assist user to assign CRM roles from the Dynamics application and Live Assist roles to these users when you log in to the CaféX Admin Center.