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I'm sure I'm just being naive, but why wouldn't it help? Aren't NFTs used to securely show unique ownership of some item?

The knockoff seller also has unique ownership of the knockoff. It doesn't fix anything.

You don’t really need a block chain, you can just register serial numbers on a legitimate website. This was solved early on with cd keys.

NFTs don't show ownership of anything, at least not in any legal sense of the word.