I've come back to this problem after the weekend and it seems to come down to this:
According to all the advice I can find (remember, I'm new to Unraid), I've been trying to copy files to /mnt/user/[sharename]
For some reason, these map to /mnt/disk1/[sharename], disk1 being the 32Gb USB stick I'm using for a data drive.
If you map a network drive to \\unraidserver\sharename\ it maps to /mnt/user/[sharename], so any files you copy fill up the USB drive rather being copied to the pool.
When the USB drive is full, all hell breaks loose (see above)
I don't know how to change this, if it's something I've done, or a bug that needs reporting.
EDIT: Just say the message about setting all shares to cache=only. I don't understand how that would work when I don't have a cache pool at the moment (SSD is in the post).
Add it to the pile of things I'm still figuring out in RC2, such as if I have a ZFS pool with (presumably) parity striped across all drives in the pool, does changing the Allocation method do anything anymore?