You can add or remove users from a Simul licence at any time.
To do so, select the appropriate licence from your dashboard:
Under "Seats" select the "Add / Remove Users" button:
To add a user, enter their email address and press "Add User":
The new user will need to sign-out and back in of your Simul Enterprise product for it to take effect.
To remove a user, select the remove_circle_outline icon next to their email address: