When to shift '94 transfer case

Shift on the fly from 2HI-4HI at just about any speed you want. 40 is a good place to consider if you really need 4WD. Stopped will work BUT it may jerk when the axles start to turn some before the axle interlock engages. Not really good for the axles and transfer case. Do NOT shift it into 4 wheel IF the rear tires are spinning and the vehicle isn't moving. The BIG BANG you hear can mean bad things.

As for 4 LO come to a stop. Put the trans into neutral and then shift from 4HI into 4 LO. Your top speed is going to be about 15 mph in 4LO.

Don't use either 4 wheel option on a high traction surface.

Not really if you want long tcase life. Two things have to happen for it to engage. First the Tcase has to speed up the front drive shaft to be able to engage it so the faster you are going the more wear on the clutch/syncronizor ring and then front axle disconnect has to engae and it assume axle is up to speed for it to work because it has no sybcronizor on it and will crunch if it is not ready. The moral is you can shift on the fly if you want at high speed but I would suggest limiting it to 25 or so to minimize wear and tear if you plan to keep vehicle long. Especailly if it is older.

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