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That is if the issue has anything to do with the internet connection (like fetching some data from Valve servers).
I have no ideas then, you could probably try to ask Steam support about this. Also you could try to intercept internet traffic from your Steam Deck and compare the requests and responses it sends and gets when logging-in with main and alt, that would certainly help Steam support to locate the issue faster, but if you don't know how to do this, that's a rather non-trivial procedure.