I am having trouble finding a way to do this via script, I would also like to stay away from Config Profile if I could.
Is there a defaults command that can change the Login Window setting to be List of Users rather than Name and Password?
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That is true, but most times that's a setting that admins don't want end users changing, which is why a config profile is usually ideal for it. Username/password is a bit more secure than just List of users since half the secret to logging in is already showing in the latter configuration.
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You can create profiles that only have one key, I think this is one of the common tools
I usually start with a Jamf or macOS server profile, unsign it edit it and then resign it with Apple Configurator.