If you have a job offer in Canada supported with a positive LMIA, then it will fetch you additional 600 CRS points for your express entry profile and you can receive ITA in the next round of invitation.
The answer to your question in the subject line is no.
As the poster above mentioned, you must still meet the minimum criteria for one of the immigration programs, even if you have an LMIA-approved jo offer.
All programs require a minimum of 12 months skilled work experience and passing a language test.
And yes, the Federal Skilled Worker program requires you to apply through Express Entry.