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להפסיק is the closest equivalent to Stop.
לעצור originally means Brake, stop moving, but can often describe the halting of elaborate processes (while להפסיק is attached to immediate actions)
- תפסיק לעבוד על התכנית הזו.
- למה?
- כי החלטנו לעצור את הפרויקט הזה לבינתיים.
לעצור can also be loaned to other contexts to add color or dramatic effect.
i don't think there's a definite answer as they often overlap, and there are some unique scenarios for both, i.e.-
לעצור can also mean "to arrest"
להפסיק is used for quitting a habit (הפסקתי לעשן for example)
as a rule of thumb, if you can use "halt", then use לעצור. otherwise, use להפסיק.