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As an American, I can tell Canadian accents from American, though I think the variance is small enough that they can easily and obviously be grouped as 'North American' vs. British or Australian/New Zealander or South African.
That said, I am only able to distinguish Newfie and western Canadian accents (roughly Manitoba-westward) from Ontario. And even though I have been to the maritimes (NB and NS), I am hazy on what distinguishing features there may be there from the Ontario 'standard'.
And honestly, my biggest cue to recognizing someone is from a western province (especially Alberta?) is their tendency to say, "Hey" instead of "Eh".