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Is something like this happening (from this guide):

Troubleshooting: When I open the link to get my Steam key itch displays a 404 error.

Solution: This will happen if you open the link in a browser that is not logged in to your itch account.
Ensure you're logged in to itch and try again.

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Update everybody: WE FIGURED IT OUT! It was an issue with the email address. Most other players' emails are probably formatted fine, so if you're having trouble it's likely one of the issues in the troubleshooting guide instead: https://itch.io/t/67604/how-to-get-a-steam-key-from-your-itchio-purchase