Because you have not yet meet the requirement to be deemed a common-law couple (one year or more of cohabiting together), and with him still being married to wife #1 (at least), he cannot apply yet. Because Canada does not recognize bigamy, his second marriage may not need to be annulled, if it never existed in the eyes of IRCC. Not sure about that, but just `throwing it out there'.
I think you are right about annulment. I don't think it's possible to annul a non-marriage. It was never a marriage in the eyes of the law, leaving nothing to annul.
But that might not be the end of the matter. There is a record of a second "marriage" in Canada and the guy would have filed proof of that marriage when applying for PR based upon it. Maybe the IRCC will simply say that they understand the second marriage was a nullity and leave it at that. But, they might want something more. It's possible that they will ask for a court order declaring the marriage a nullity. The OP's amazing (and expensive) immigration lawyer used in the past might be able to advise on that score.