Setting an App as default for a profile doesn't seem to work. I created a custom Sales app. I set this app as default for my user's profile but when he logged into Lightning for the first time he was brought to an entirely different app. When I logged in "as" this user I was brought to my custom Sales app as expected so I can't explain what happened. Its almost as though Lightning randomly selected an app to open (we have about 20) for him and completely ignored the default. This user has never logged into my sandbox before so there is no reason this would have been the last app he visited either.
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Is it possible that the user's app preferences from the production org somehow came over when you refreshed the sandbox? If you can duplicate this with a net new user in the sandbox, the best course of action might be to log a case and let a support agent troubleshoot it with you. Feel free to share your case number here once you get that going.