Your idea is seriously problematic:
- Windows 10 only boot from NVMe drives with UEFI installs.
- UEFI Windows installs requires at least UEFI v2.3.1c.
- Mac Pro 5.1 is not UEFI, but EFI and an ancient one, EFI v1.10. No one knows why Microsoft overlooked this and permitted UEFI installs with MP5,1.
- Windows 10 installed via UEFI mode running in a Mac Pro causes constant re-signing of the Mac Pro SPI, the SecureBoot certificates inside the NVRAM volume, this is one of the causes of the constant bricking of Mac Pros. MP5,1 EFI was never intended to work with UEFI Windows, just CSM.
- BootCamp assistant won't work if you use an UEFI install, you will need to reset the NVRAM every time you want to go to macOS.
It's not worth the risk, while some people never had the problem, every week someone asks helps to un-brick MP5,1s.
If you want to go for this anyway, the risk is yours, you will have to do a clean UEFI install from a USB key to a SATA drive, then clone it to the NVMe drive, since Windows don't install to external drives.