This is a scale and mass issue.
The candle wick has a relatively small mass, so the small amount of water on your fingers absorbs almost all of the heat energy without much turning to steam, and a layer around your finger stays below 100C.
The pan has a relatively large mass, so it can transfer a large amount of heat energy into your wet oven mitt. The water absorbs enough to turn into steam, which then expands to fill the space around your dry hand. That steam then imparts all of that heat energy to your hand before condensing back into water, which burns you.
TLDR: Specific heat of transformation is a bitch.
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