Dear Colin - Valley IT,
Good day! Thank you for posting to Microsoft Community.
Typically, to log in as a user in Microsoft 365, you will need to have the user's login credentials. If Security Defaults are being enforced, then the user will need to use two-factor authentication (2FA) to log in and user must cooperate with you to have access for the mailbox. However, as a Global Admin, you can assign a full access delegate permission to your account from the admin center which doesn't require you to use user's credential and two-factor authentication (2FA) to access their mailboxes. This permission will allow you owner level access, so that you can easily open the mailboxes without needing the user’s password or MFA token. To do this, kindly go to Exchange admin center (https://admin.exchange.microsoft.com/) --> Recipient -->Mailboxes --> Select the user account you want to open or access -->Delegation -->under Read and mange (Full access) option, click on Edit -->Add members -->Select your account -->Confirm. You can refer to the screenshot. Also refer to Manage permissions for recipients in Exchange Online | Microsoft Learn
Once you have assigned Full access delegation to your account, kindly Sign in to your account -->click on your profile picture -->Click Open another mailbox -->Type the email address of the other mailbox that you want to open, and then click Open. Then, it will open in a separate window, allowing access to the other mailbox.
This will allow you to access as owner without having the credential or 2FA of the user account.
I hope this will help. If you have other questions or I have got you wrong, please feel free to let me know.
Thank you for your precious time. Have a nice day.
Sincerely,
Libeamlak | Microsoft Community Moderator