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A high class call girl will work for herself - maybe an agency. They will work when they want, keep most of the money, decide if they want to be with a client and usually have sex in an apartment or hotel. It will be like a date with a definite happy ending. With escort you can also enjoy free time and you can make her/him a travel companion.
Street corner prostitutes sell sex for a lower price. Sex for money is prostitution plain and simple.
Call girls and escorts work for agencies that monitor them. These women sell their time, their experience and a professionalism that women who work corners don't.
Also call girls and escorts tend to market to a higher end client, who is looking for a companion as well as potentially a sex partner. Call girls and escorts accompany clients to events and dinners, not just fumbles in a hotel room.
So the difference is huge.