Assume the processing time for an LMIA will be around 4 months.
Generally speaking, your chances of getting a work permit approved are somewhat lower if you apply from Canada (vs. applying while you are outside of Canada).
Impossible to comment on the chances of PR since there are so many factors that go into determining what it takes to apply and who is selected. Recommend you calculate how many points you have under the Express Entry program. If you score more than 440 points, you have a very high chances of being selected.