Literally, it means to remove something from the heat so that the liquid is no longer boiling. But I think you know that :)
As an idiom, if s'thing or s'one has gone off the boil, it/they are not currently as good/enthusiastic/popular as you were previously. A way of thinking about it is, they're not as 'hot' as they were before. :)
Example taken straight from a sports news headline: "Ross Barkley has gone off the boil... the England midfielder has provided just one assist in his last 66 matches for Everton"
To me, it's quite a 'gossip magazine' kind of phrase. Incidentally, I googled for examples and most of them were article headline puns about cooking shows! ^_^
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