Start here:
http://www.canadavisa.com/canada-immigration-discussion-board/spousal-sponsorship-t46995.0.html
Ignore the processing times that were written in the post, because it's nearly five years old. The links in the post should still be valid though.
You must decide if you want to submit an Inland application or an Outland application (both are described in the link above).
You will need to gather a fair amount of documents that will be included with the application package (such as copies of his birth certificate, your passport identity pages, your Option C from CRA, copies of previous divorces, etc.). You will find everything that you need, here:
http://www.cic.gc.ca/english/information/applications/fc.asp
(this is for an Outland application, which is generally the preferred method since it is usually much faster than an Inland application).
If you decide that you do want to submit an Inland application, he would need to come to Canada and remain in Canada as a visitor, but it currently takes ~ 2 years to get through this process. The Inland package is, here:
http://www.cic.gc.ca/English/information/applications/spouse.asp
The PCC, is the police check that he will need.
Besides the applications and related forms, you will also need to submit proof of your relationship, NOT just a copy of your marriage certificate. CIC (Citizenship and Immigration Canada) needs to see that you were in a genuine relationship prior to your marriage too. People usually send photos, cards, letters written to/from each other, emails, etc., but again, you will find out more as you peruse the many threads here to help you.
Good luck!