Docking with Stations, Exiting Pilot Seat while in Space
Docking with a station, and exiting the pilot’s seat are both done the same way: Use the same button you would to exit the pilot chair (“E” key on PC keyboard). Hold the “E” key down to step out of the chair, even when in orbit.
Before docking with a station or ship, it needs to be targeted by hitting the E key.
You’ll have the option to hail the station/ship. Only when you are close enough to the ship will you get an option to dock with it.