My customer has many people that have never used ODfB, in this scenario, is it ok to use the Move the contents of Documents to the new location setting in the GPO or do we really need to use Robocopy? If so, does anyone have guidance on its usage for this scenario? I don't have any experience with it.
As clearly stated in the article about Move the contents of Documents to the new location, "Leaving this setting enabled could result in data loss when the contents of the Documents folder is merged with the OneDrive for Business sync folder, if there are files with the same name in both locations."
If this is not the case, i.e. you are absolutely surethat there are not files with the same name in both locations, then you can safely check that setting. I have done it without adverse consequences.
Instead, FYI, I have had troubles with some files that you frequently find in Documents' subfolder, such as PSTs and VM disks. Be careful...