1. LE = Luxury Edition. You got the model with all the goodies.
The car tends to overheat when 1 fan is down. Happened to my V6 on a trip from NY to Missouri. Once I replaced the fan, it was fine.
2. I've used the Haynes manual. You can find a used Toyota factory manual on Ebay for a reasonable price. I paid $12.00 for mine.
3. On the V6 engine (2VZ-FE), the PCV Valve is located on the rear valve cover, towards the back.
4. Changing the plugs and wires for the first time will be difficult. The good thing is that once you've done it, you never forget to do it. It's suggested that you lift off the intake in order to access the rear 3. I managed to change them without having to do that, but it is time consuming. If you plan on attempting it, may I suggest you get yourself some "u-joint" socket adapters to help compensate for the lack of clearance. The key is to take your time and do one at a time. If you are pressed for time, then you should take it to a mechanic.
5. Might need a tune-up, might be a misfire; not sure. A tuneup should resolve the problem.
6. $750 for a running V6 LE? I think you got yourself a very good deal. Once the maintenance issues get worked out, you will automatically make your money back in 2 months of driving. Regarding the advice at Pep Boys, you'd be better off getting new rotors and pads and doing it yourself. If the car stops when you press the brake, then the calipers are obviously working. You might want to see if it pulls on one side. Ultimately you should check them yourself. If you never changed brakes before, make it your business to learn. You will save quite an amount of money when you do it yourself. On my 89 V6, I've only had to replace 1 rear caliper. To play it safe, I replace both rear calipers. Paid off in the long run.
7. Toyota has a tune-up kit for the 2VZ-FE (forgot the part number though). The kit I got from my friend (a former Toyota mechanic) contains (6) red 9mm Sumitomo wires, Toyota platinum plugs, and the Dist cap & rotor. It was a bit pricey, but Toyota quality exceeds anything you would find at a Pep Boys or other retail auto store.
check for OEM Toyota parts at
http://www.toyotaandlexusparts.com
If not, you can get 8mm NGK wires.
Good luck with the car.