Currently Teams desktop does not support multiple accounts, currently you can only log in with one enterprise account and add other personal accounts in Teams.
But features like multi-tenancy and multi-account in the new Teams enable you to collaborate more effectively across organizational boundaries, while staying signed in to multiple accounts and receiving real-time notifications, no matter which account is currently in use. You can seamlessly interact with users across multiple accounts and organizations without leaving calls or meetings, ensuring your workflow isn't interrupted.
The new Teams is currently in preview. To learn more about new Teams application for Windows, please check https://techcommunity.microsoft.com/t5/microsoft-teams-blog/introducing-the-new-microsoft-teams-now-in-preview/ba-p/3774406
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