I've spent a couple of hours testing a few different scenarios and this is my result:
I've formatted both disks tested back to a single exFAT volume in Windows using a USB to SATA reader before beginning.
Original USB stick in laptop: Boots to Unraid
Original USB stick in server:
a) With nothing connected to SATA card: Boots to Unraid
b) With SSD connected to SATA card: Does not boot, freezes on blinking cursor
c) With new HDD (SATA2) connected to SATA card: Does not boot, freezes on blinking cursor
New USB stick with fresh Unraid 6.8.1 in server:
a) With nothing connected to SATA card: Boots to Unraid
b) With SSD connected to SATA card: Does not boot, freezes on blinking cursor
c) With new HDD (SATA2) connected to SATA card: Does not boot, freezes on blinking cursor
e) With SSD connected to USB 2.0 SATA enclosure: Boots to Unraid, disk seen in UI
f) With SSD connected to USB 3.0 (on USB 2.0 port) SATA reader: Boots to Unraid, disk seen in UI
g) With new HDD (SATA2) connected to USB (on USB 2.0 port) SATA reader: Boots to Unraid, disk seen in UI
No USB stick in server:
a) With nothing connected to SATA card: Blank screen, keyboard responds
b) With SSD connected to SATA card: Blank screen, keyboard responds
c) With new HDD (SATA2) connected to SATA card: Blank screen, keyboard responds
If the SATA card is interfering with boot order then it behaves differently depending on whether the UNRAID USB stick is inserted or not.
It looks like I can use the USB 2.0 enclosure to add my SSD but since I want it as a cache drive this seems non-optimal.