1. Wind Cries Mary, by The Jimi Hendrix Experience
This is not one of Hendrix's more rocking shredding tunes, but I still feel it is one of his absolute best. He shows just how much blues influence really does go into his playing without an overabundance of fuzz or whammy. It's something you can get lost in the groove of and let go of yourself in; especially during the main chord progression. Honestly, this is not a bad song for blues beginners to learn on guitar.
2. Comfortably Numb, by Pink Floyd
This is a rather powerfully emotional song on multiple levels. Even if you don't have the drug problems that the character in the song has, if you've suffered from depression you know just how the concepts mentioned in the song can feel. It does not take long for it to cut you right to the bone and give you feels. Layer that on top of one of David Gilmour's greatest guitar solos of all time and you've got a tune that is a masterpiece and played constantly on the radio for damn good reason.
3. Man on the Silver Mountain, by Rainbow
This is one of Ritchie Blackmore's most famous guitar riffs of all time. It gets ingrained in your head and absolutely will NOT leave no matter how hard you try. Anyone who is a 70's or 80's metal head knows this tune, as it is also where Ronnie James Dio made his big time band debut. It's one of those songs that makes you feel like you're at the beginning of a fantastic amazing adventure of AWESOME. To be honest, given what all is in Rainbow's catalog your feeling would not be wrong at all whatsoever.
4. 2112, by Rush
Like big long grand rock operas? Look no further! This Rush classic clocks out at over 20 minutes and it is the most epic 20+ minutes you could ever hope to spend your life on. In a dystopian future a boy discovers a guitar and how to play it, but when he shows it to the people they shun him and kill him just because he is doing something outside the norm and challenging the ideals of the modern society they have. Add that onto some big riffs, wailing vocals, and thundering drums and you have an epic.
5. I Wanna Rock, by Twisted Sister
What do you want to do with your life? I WANNA ROCK! Who doesn't? This is one of the ultimate 80's metal songs of teenage rebellion against parents, teachers, and the establishment at large. Twisted Sister may have looked absolutely ridiculous, but they understood kids and their problems better than any adult ever will regardless of the fact that they were once teenagers themselves. It definitely reflected in their music and I Wanna Rock is the best example of that besides their other hit We're Not Gonna Take It.