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I recommend you go back a fair bit to J. Michael Straczynski's work on the book. It's, for the most part, an extremely good run on the character that features both classic villains and supporting characters as well as introducing a bunch of new, more minor ones. It also introduces a lot of important mythology for the character that's often overlooked. It's a pretty long run, so I recommend you read it through two really big volumes here (http://www.amazon.com/Amazing-Spider-Man-Ultimate-Collection-Book/dp/0785138935) and here (http://www.amazon.com/Amazing-Spider-Man-JMS-Ultimate-Collection/dp/0785138943). There's three other volumes, but I suggest that you not bother with them, as they were done during a period where Marvel's editor mucked with the Spider-Man book a lot and effectively ruined the story; they contain some of the worst Spidey stories in recent times and the central plot of the run was effectively wrapped up by than anyways.

After that I suggest you skip ahead to Dan Slott's work; start with Brand New Day and end with Ends of the Earth, reading all the stories between there. It's overall not as good as JMS's work, but it's an excellent run on the story that captures everything great about Spider-Man while also introducing a new status quo. As for Superior Spider-Man, I don't really recommend it; it's not horrible, just not nearly as good as what came beforehand.

As for Iron Man, I suggest going back to Matt Fraction's Invincible Iron Man run. It's a great run on the character and pretty much all of Iron Man's cast appears, so it's a good primer on the series and it's mythology.