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Going from a lighter color to a darker is doable, but it takes a bit of trial and error to get the process and the color right. Unless the trim has been heavily sealed over the original stain, a light sanding may be all you'll need to get it to accept more stain. The more you know about the existing finish, the better the results will be: is it an oil-based or latex stain; if there is a finish coat, is it polyurethane or something else. A thin coat of shellac will take a stain, but other finishes probably won't.
The thing that is impossible to tell without trying is what color a darker stain will be once it is applied over the existing color. That is what will take the most trial and error, but if it messes up then you can always sand, prime and paint.
Good luck!
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