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The red wire goes to the starter (Main battery power) you can see the red connector on the starter in your photo just below the intake manifold. The only place you will find a cable with the proper starter end connector is from the dealer of a wrecker.
While it makes no difference to the car. It is generally safer to disconnect the NEG first. If you remove the POS first and accidentally short the wrench to the car body it will short out. If you remove the NEG first this is not an issue as the body is already connected to NEG. The Haynes manual also recommends NEG.
BTW my 95 has two black wires in that location one it the main engine/starter ground and the other connects the body beside the radiator.