When you apply for FSW/EE, the underlying premise is that you are "intending" to reside anywhere in Canada except Quebec because, the logic goes, QC have their own system and if your intention is to live there then you should just apply through their system and all will be well. Sounds simple, right? Now, of course the reality is that not all immigration streams are created equal: some are easier to get in than others, and some may be closed while others are open.
Strictly speaking, if you apply to one stream simply because it is easier than the one that you would normally apply to, and your "intention" is only to use it to circumvent the system and go live in that other province you -implicitly or explicitly- said you wouldn't go to, then this is misrepresentation. However, since it's mostly about "intentions", which can be hard to prove and which could differ from one's actions for a great number of reasons, people do it and get away with it all the time.
When you land as a potential PR, CBSA officers are instructed to ask you about your intended destination. If what you tell them contradicts your application, they have the authority to deny you your landing and make things very unpleasant for you, as you're practically admitting misrepresentation to them. If, on the other hand, they ascertain that your intentions are sincere (or don't even ask) and allow you to become a Permanent Resident, then your Mobility Rights are protected by the Charter of Rights and Freedoms and you can go live anywhere you want at any time, starting that instant after you land. In general however, people would cautiously advise you not to move right away and at least try to spend a few months and show effort in settling where you said you'd settle, but all this is just so you have enough evidence in case your "intentions" get challenged at any point in the future. To be fair, I have yet to find one PR who got his citizenship denied or his PR revoked on this basis alone.
Best of luck with whichever process you choose!