I would highly recommend the 44 years of the Amazing Spider-Man DVD-ROM set as it's a sweet way to catch up on all of the issues of Amazing Spider-Man. It's one thing to read summaries on Wikipedia or in Spider-Man the Ultimate Guide but it's so much more fulfilling to read all of these old issues one by one and witness the evolution of Spider-Man. While alot of the 1990s issues are garbage, I would highly recommend the Stan Lee/Steve Ditko era, which is one of my personal favorites. I enjoyed John Romita's but never loved it the way some have. His son, John Romita Jr., is a fantastic artist, especially in the first part of J. Michael Straczynski's run (pre Sins Past of course).
I would personally recommend the DVD-ROM as well as the Marvel Essentials Line. Although the reprints are in black and white, there are a lot comics for not too much money, and the color quality from the 1960s and 1970s is lacking anyways. The artwork is almost enhanced by the lack of color. You can also collect all of the recent Amazing Spider-Man by J. Michael Straczynski and Brand New Day in trade paperback and hardcover.
To Recap-
44 Years of the Amazing Spider-Man (Amazing Fantasy 15, ASM 1-530, Annuals 1-26)
http://www.amazon.com/Amazing-Spide...ollection/dp/B000HKIM7Q/ref=pd_bxgy_sw_text_c
Essential Spider-Man (Black and White Reprints)
http://www.marvelessentials.com/
The JMS run of Amazing Spider-Man (A list I ALSO wrote myself)
http://www.amazon.com/The-J-Michael...n/lm/RAQ9JYSC6XD3L/ref=cm_srch_res_rpli_alt_2
The Brand New Day era (After the JMS Run)
http://www.amazon.com/Amazing-Spide...lm/R32NCY7BW9SN37/ref=cm_lmt_srch_f_1_rsrsrs0
Also recommended (something I want myself) is the ASM omnibus, which collects every Steve Ditko issue of Spider-Man in one MASSIVE hardcover. Kind of expensive, but so awesome. Only a hardcore fan should buy this, not a first-timer.
http://www.amazon.com/Amazing-Spider-Man-Omnibus-Variant-Version/dp/0785125094/ref=cm_lmf_tit_1
Also recommended is Ultimate Spider-Man, a modern take on the character, which I love.
http://www.amazon.com/Ultimate-Spider-Man-TPB/lm/R3E5IS91UOCORZ/ref=cm_lmt_fvlm_f_2_rlrsrs0
And if you're interested in further stories of Gwen Stacy, Spider-Man: Blue is a good read.
http://www.amazon.com/Spider-Man-Bl...=sr_1_1?ie=UTF8&s=books&qid=1250459814&sr=8-1
Mark Millar's Marvel Knights Run was really fun to read and I desperately want the Hardcover but can't find it anywhere within my price range. (MKSM 1-12)
http://www.amazon.com/Marvel-Knight...=sr_1_1?ie=UTF8&s=books&qid=1250460495&sr=8-1
In terms of film/television, I love love love Spider-Man 1/2 as I think they nail nearly everything great about Spider-Man. Not 3. 3 Bad. 3 Very Bad. Grrrr.
And the Spectacular Spider-Man is supposed to be a very good cartoon adaption of Spider-Man but seeing as I'm not 9 and cannot wake up before 11:30 on a Saturday morning, have only seen the first 3 episodes on my computer. It's a very good adaptation if anyone's interested.
http://www.amazon.com/Spectacular-S...ef=sr_1_5?ie=UTF8&s=dvd&qid=1250460313&sr=1-5
I also really enjoyed Spider-Man the new Animated Series on MTV. Very slick animation and fun voice acting. I don't think anything has ever captured Spidey's movement the way this show did.
http://www.amazon.com/Spider-Man-An...ef=sr_1_8?ie=UTF8&s=dvd&qid=1250460313&sr=1-8
or watch it online at Hulu-
http://www.hulu.com/spider-man
FINALLY- Stay away from Spider-Man-Torment. It's a five-parter created by Todd McFarlane and it is quite possibly one of the most ******ed stories ever. It's so slow, boring, unfunny, undramatic and artistically incomprehensible that I wanted to drill straight through my forehead after I read it. Same with Clone Saga, Maximum Carnage, Sins Past and One More Day. Awful stories, each of them.