Surface rust will always develop on the pad swept area of the rotor's face, value rotors or premium [sans carbon rotors]. For the non-swept surfaces, you can purchase 'premium' rotors that are coated to help prevent rust from showing on those parts, but I have never really heard of an [iron] rotor that does not develop surface rust on the pad swept area.
Seized pins can be prevented by replacing and using new rubber boots and pin bushings and the correct grease whenever working on the brakes (Of course clean out as much of the old grease as you can from the bore in the caliper bracket; I use a combination of q-tips, a paper towel wrapped screwdriver, the pin itself and brake parts cleaner). I have found that O'Reilly's 'BrakeBest' brand to have great prices on the rubber boot pin kits and the quality seems pretty good compared to my other go-to brand of Carlson. Rubber will age over time and may not seal as well against the lips on the caliper brackets or pins if just cleaned and re-used.
I recommend against using any of the dark-colored 'CRC Synthetic Brake Grease' on caliper slide pins and boots; that stuff will swell rubber parts and can lead to seized pins. The CRC stuff I have found works fairly well in between shims and the backing plates (if you have the loose clip on style shims instead of the bonded type). I have been using Napa Sil-Glyde with great results on slide pins.
Specifically regarding that seized rear caliper, sometimes it's not much more to purchase a friction-ready caliper, which includes a rebuilt caliper and bracket; I've found the prices on single brackets to be close to purchasing a complete caliper. And also, many times there is a difference between the top and bottom pins (usually length); install these in the wrong location [along with a rubber-swelling grease if the pins have bushings on them] and it'd be quite easy for the pin to then seize in the bore.
Some premium pads will come with the necessary abutment clips/hardware that should be replaced, Raybestos Advanced Tech, Bendix CT-3, and almost any Centric pads [even their economy pads] I've used in the past, so you may just be able to purchase pads that include these and worry about purchasing a rubber pin boot kit and bracket/caliper assembly separately.
Hopefully everything works out. If you run into anything else, don't hesitate to let us know, but it seems like you're on the right track. Trust me, it so nice to have properly working brakes after dealing with and getting used to ill-working ones.