As others have said, youtube.com/purgegamers is a great place to start. He does a tutorial about purchasing starting items and a tutorial on all the items in the game. Plus he does a game with commentary for all the heros...find the heros you like and watch them. He will explain item builds / skill builds / how to play the hero.
Join the Giantbomb channel in game, we generally have a good amount of people idling in there and they probably would be more then willing to teach / play some games with you.
Some basic tips I would give:
Pick "easy" heros at first. These are heros who can be viable the full game without needing you to rely on getting a ton of farm. If you pick someone like Faceless Void and you do not get 200+ CS, you will be useless and lose the game for your team. So stick with guys who make a major difference in fights based on their abilities not items. Some I would recommend: Lich, Lion, Windrunner, Tidehunter, Shadow Shaman, Venomancer, Vengeful Spirit, and Skeleton King. Once you feel comfortable with positioning / last hitting...then start trying some of the soft carries like Drow Ranger, Mirana, Weaver. Then when you feel like "Wow I am really good at last hitting and usually am around 100 at the 20min mark" then pick up Anti-Mage, Broodmother, Faceless Void.
Items: Generally recommended items will work until you figure out what is best. But try to build items that let you support your team. Stuff such as Mekanism, Drums of Endurance, and Pipe of Insight. All of which make your team better in fights rather then them relying on you to get the kills. All of those heros I mentioned except Tidehunter / Skeleton King (generally build them tanky) should pick up a Mekanism ASAP to heal your team. Say you are playing Lich, you don't need to be super gosu and kill everyone. All you need to do is stay towards the back, slow the enemy team with your Q, pop your ultimate right when the team fight starts, then activate your Mekanism as soon as everyone starts taking damage to heal them all. If you do this, you are instantly MVP on your team because you contributed majorly to the fight.
Dont be afraid to ask questions. Sometimes people think if they go "What should I build on Lich this game?" that their team will just go "LOL NOOB!" If they do, then your team deserves to lose. But most of the time people will be pretty cool and say "Well just worry about purchasing obs wards and build a mek when you can." There have been a ton of games where a new player will not know what to do, then will buy the wrong items, then 45 min into the game they get yelled at for being bad and they say "Well I didnt know!" rather then just asking for some advice.
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