By all means teach the use and function and flaws of the safety on firearms. Then try to go through all of the different types of safety. You'll need a lot of time.
As others have said, it all depends on circumstance. As a Mauser '98 shooter you'll know that trying to manipulate a "wing" safety under a low slung scope is a P.I.T.A, bolt up on a chambered round in those for me. Actually that is my standard practice with all of my bolt actions both when hunting alone or with others with known and trusted abilities.
Mind you, I'll only have a round chambered when I'm sure of a shot being imminent. I will walk with an empty chamber the rest of the time and trust my ability to quickly chamber a round in the event of surprised game, ( or hunter ).
. The exception being if I'm hunting with my lever-guns, I do trust the Winchester "half-cock" safety.
Hunting with a "new" bloke, I make sure they have the bolt closed on an empty chamber. I'd rather they miss a shot than shoot me.