Some info from my flying days in a similar jet:

1. The F-14A had a handle in the aft cockpit against the port bulkhead that could be placed fore or aft, called the command ejection selector. It was labeled "Pilot/ MCO" (Missile Control Officer, an early name for the RIO). In the forward, pilot position, the RIO could eject alone. The handle was selected to there on deck and when non-qualified people got rides in the back seat. When I selected the aft, MCO position, either aircrew ejecting would eject both people. When both people ejected together, first the canopy jettisonned and the RIO went, and then, 0.4 seconds later, the pilot went (to prevent the RIO from getting a face full of the pilot’s fire). The RIO seat had 5 rockets on the left side and 4 on the right, so it biased to the right, coming out. The pilot's seat was 4L/5R, so it biased to the left.

2. Normally, the canopy's jettisonning was the first part of the standard ejection sequence, but there were three times the crew might want to launch it manually. Each crew member had a yellow handle in front of his right shoulder that would jettison it.

A) If you had to emergency ground egress, like you were on fire badly, blowing the canopy might save a little time scrambling out. On the flight deck, though, I'd be worried about hitting someone with it, in that case.

B) If you had bad smoke and fumes in the cockpit, blowing the canopy would solve that issue, although it would also certainly introduce all kinds of new problems. I once had a small electrical fire whose smoke was burning my pilot's and my eyes badly, but we talked about it and decided not to shuck the canopy until we were absolutely desperate. We got the fire out and came home fine.

C) In an upright flat spin, the aircrew, probably the RIO, was to jettison first, then command eject. The pilot will likely be unable to do either because, sitting 6 feet farther forward, the eyeballs-out G from the spin will likely pin him forward against his instrument panel, unless he gets his harness locked very quickly in the beginning of the spin. One of my pilots got into a fully developed flat spin, and he was indeed stuck with his face up against the turn needle, which was lucky because he could then enter the correct anti-spin flight control inputs and eventually save the jet.

Also, IMO, the biggest factor in two aircrew landing miles apart will the barometric altimeters in the seats being calibrated slightly differently, triggering automatic seat-man separation at different times, altitudes, and winds.