Okay, I was completely confused about your setup. You kept mentioning SSDs and HDDs and never mentioned a 250GB SSD specifically, and weren't clear about what drives did what. I thought it was just the PARTITION that was small for your boot drive, not the actual drive, and thought it was on the 2TB drive. I never realized you had an SSD for boot and the 2TB drive was a mechanical drive just for data, and you kept mentioning the backup of the boot partition and I was never clear about that. Why in the world do you want to boot to a mechanical drive and run your OS on that? Even an old SSD like the BX100 will be faster.
What's listed in Hard Drive BBS Priorities? What happens if you set Storage Boot Option Control to UEFI first? I don't really think either of those matter, just throwing things at the issue because it's really odd. No idea why the SSD isn't listed as a boot option.
The only thing I can think of is that the BCD on the 4TB drive isn't configured properly, or the boot files didn't get copied properly to the EFI partition, so when you try to boot to that with both drives connected it doesn't look at the correct location. The 0xc0000025 error is related to missing boot files. Perhaps it is set to look for a partition on the SSD that doesn't exist because it's MBR, but it falls back to the HDD if the SSD isn't connected. Unplug the SSD and boot to a Windows installer, and go through the repair functions with bootrec and copying the boot files with bcdboot, and rebuilding the bcd. May need to completely blow away the BCD and recreate it, and/or remove the EFI partition and recreate it and copy the files.
Which drive did you clone onto the 4TB? It should have been the SSD being cloned to it, so you would be getting your current OS configuration, then converted to GPT and your other partitions created.
What's listed in Hard Drive BBS Priorities? What happens if you set Storage Boot Option Control to UEFI first? I don't really think either of those matter, just throwing things at the issue because it's really odd. No idea why the SSD isn't listed as a boot option.
The only thing I can think of is that the BCD on the 4TB drive isn't configured properly, or the boot files didn't get copied properly to the EFI partition, so when you try to boot to that with both drives connected it doesn't look at the correct location. The 0xc0000025 error is related to missing boot files. Perhaps it is set to look for a partition on the SSD that doesn't exist because it's MBR, but it falls back to the HDD if the SSD isn't connected. Unplug the SSD and boot to a Windows installer, and go through the repair functions with bootrec and copying the boot files with bcdboot, and rebuilding the bcd. May need to completely blow away the BCD and recreate it, and/or remove the EFI partition and recreate it and copy the files.
Which drive did you clone onto the 4TB? It should have been the SSD being cloned to it, so you would be getting your current OS configuration, then converted to GPT and your other partitions created.