I was actually in the same shoes as you. Although you should make an assessment of what is more important to you.
For me, the PhD was more important than Canadian PR. So, I took my fully funded PhD offer and came to Canada and then applied for PR once I was in canada. I got PR by the end of my first year in PhD. Although as a PhD candidate at one of the better universities in Canada, the benefits I received were not too much lower than for a PR. If you have a family, you become eligible for child benefit and other benefits after a period of 18 months etc. The only difference is you have to pay health insurance. So, in terms of benefits there are some differences, but not too much.
To me, the more important question is, what kind of career do you want? As you know (and you mention) once you leave academia, it is much harder to come back.