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Is there a way I can alter the ToC styles so I get the page number first, then the heading text, instead of the other way around?

When editing a ToC style there's no way to insert the page number into the line; at least, not from any menu: there's a number, 24, that can be selected and moved to the top, but this simply has no effect on the generated data.

Or am I missing something?

Unless your text naturally runs from right-to-left (eg: Hebrew), I'm afraid this isn't something you can do at this time. I'll file a feature request.