However, I know there's such a thing as a "volunteer visa." So what's that about then? Hmmm . . . .
Peedal's right. The fiance does not have the immigration status of someone on a settlement track, and therefore cannot work, in the same way that the fiance cannot claim bereavement. The grounding for paid or unpaid is because if you went to a job sweeping the floor at Tescos for no pay, you would be scooping somebody out of a job, and further the IND suspects that you would be reaping *some* benefit somewhere for doing unpaid work. So no paid or unpaid work is the rule.
To your other question, about the volunteer visa: these are concerned with registered charities. They are entry clearances issued exceptionally for periods up to 1 year to do a specific job at a specific charity. Because they are exceptional, they don't really fall into the categories above, and the rules are vague for the instances where an entry clearance was granted in another category.
So if a fiance were to take up work for a properly registered charity, there's a case that can be made that she is not in breach of her conditions - because volunteer work is permitted for those who are not on a settlement track. Similarly, there's a case that can be made that she's an illegal entrant because volunteers intend to leave the UK after 1 year.