The engineering team is continuing to work on adding support for multiple accounts on desktop clients. We will first launch support for 1 work/school account and 1 personal account so users can enjoy Teams for work and personal side-by-side. Windows and MacOS. Support for multiple work accounts is still being worked on and will come at a later date.
You can track status via the roadmap here: https://www.microsoft.com/microsoft-365/roadmap?searchterms=68845.
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Notifications fail to arrive when using multiple accounts on android and iOS. I noticed that I would not receive notifications for incoming calls even for the currently active account in teams. I had to log out both accounts and only log in with one account to get reliable notifications again. Still not even close to be a workable solution
Pinning the entire document library is supported today. Learn more here, https://support.microsoft.com/en-us/office/add-a-sharepoint-page-or-list-to-a-channel-in-teams-131edef1-455f-4c67-a8ce-efa2ebf25f0b.
We currently do not support pinning a specific folder, but we are considering this feature.