Many thanks, jefro, for your suggestions. They prompted me to check whether the partition of the USB drive had its boot flag set. It hadn't, and so I set it. The BIOS itself was quite awkward to set as you suggested, as sometimes it would show my two hard drives as UEFI (without boot) and no legacy drives at all, and sometimes as legacy, along with the USB drive seemingly regardless of how I had saved it. Eventually I put his last at the top and got it to stick, and then the machine would boot from the USB!
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