If I understand correctly, the new releases of Windows 10 will allow you to do clean installs using the prior OS License Key. Since we all know the EULA states the prior OS is no longer usable, I do not know what might happen to your old install if you were to try to boot to it after you have done the upgrade.
Whether a License key from a 32 bit version will work for the 64 bit version is hard to say. If it were to be an OEM license or perhaps one of the Student Licenses, it may not. But I suppose you will find out during the process.