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Try doing it in two goes; open toc.ncx, and make sure the replacement setting is set to Current file.
Now first leave the first letter in in the first word capitalised and lower all the letters after it:
Find: <text>([A-Z])(.+)
Replace: <text>\1\L\2
Then capitalise the first letter of each word:
Find: <text>(.+) ([a-z])
Replace: <text>\1 \u\2
you'll need to click "Replace All" more than once (until it says "No replacements made"), the number will depend on the number of words in the longest title; not elegant, but seems to work.
I guess there'll be some corner cases, e.g. a capitalised "The" or "To", but you can replace those easily afterwards.
Note that if you re-generate the toc again in Sigil all those changes will be gone, so make sure you don't need to generate the toc again before doing that.
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