Well, to start, welcome to the VG section of the forums! We're always glad to see more people getting started with VG.
Second, if you're a bit rusty on your EV knowledge, feel free to check here for more knowledge: http://www.pokebeach.com/forums/thread-ev-training-guide--102854
You're also going to want to download Pokemon Online as a way of battling other people. It's basically PlayTCG except it's PlayVG: http://pokemon-online.eu/
I find the best way to start playing VG is to simply dive right in, as doing a lot of battles will quickly teach you what you need to know. Here's the list of OU Pokemon, which are like Tier 1 decks in TCG: http://www.smogon.com/bw/tiers/ou
Lastly, I'll be glad to go on chat or Skype sometime to teach you any basics or anything you need to know. Hope you enjoy VG!