I HDD booted fine from the ODD when it was in the laptop alone, so clearly it isn't that.
As I said, all configurations attempted.
Worked fine with SSD or HDD in either port, but not with both installed together.
Clearly, that was tested when I had Win 10 installed on the HDD.
The problem occurs only when both drives are installed, regardless of which port the HDD is in, and regardless of whether it has Win 10 installed or not.
The system simply doesn't want to boot correctly, or recognise the HDD when the SSD is installed. It'll display in BIOS and Device Manager, but no reference to it in File Explorer or Disk Management. Plus the 15m boot time is clearly not normal.
As I said, latest BIOS and firmware installed.