Just been updating my wee list of master mariners from North Walls and Brims. You may know this occupation better by the term sea captain. They were in charge of ships in the commercial fleet rather than the Royal Navy, some sailing around the world, others in coastal waters only. You can find the Walls and Brims group by following this link. Not a bad list for a rather impoverished part of Orkney.
I’m only working on those who became captains and were listed in the 1861 census in Walls (or their parents were). There were far more from the parish who went to sea as 1st or 2nd mate, able seaman and so on.
The National Archives at Kew have information on researching officers in the merchant navy