It is the same as the process for anyone else.
If by 'without a job' you mean 'without arranged employment in Canada', you will get more CRS points for having valid arranged employment in Canada, but that doesn't mean your other characteristics won't provide you with a high enough CRS Score to receive an Invitation to Apply (ITA).
If by 'without a job' you mean 'you're currently unemployed', unemployment doesn't factor into Express Entry - you are evaluated based on relevant work experience completed in the last 10 years, not whether or not you're currently employed. Hope this answer helps.