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It's pretty complicated, but basically each time you kill a Pokemon you gain evs from them. For every 4 EVs you get, your pokemon will gain one point in that stat. So say I want to get my Chanseys HP as high as possible, I'll go to a place where I encounter whismurs a lot. For each whismur I kill with Chansey ill get one HP EV. If I kill 40 whismur, I get +10 to the HP stat. The stat effects only happen when you level up, and they may not all add on at once, but they'll gradually spread out so by the time you hit level 100 your pokemon will have the extra stat points. If you train your pokemon at around level 50 you'll see big jumps on level ups, such as +20's to certain stats assuming you do a lot of training.
Use Google to find out what pokemon hive out what EVs. Be aware that you only have 512 total EVs to distribute, and 252 max for a single stat. So if you keep track you can get +63 in 2 stats, which is huge. Or you can spread them out more evenly. Personally I cbf keeping track so I just go and kill a hundred or so pokemon for a certain EV then move on.
And if your pokemon has a macho brace, they get double the EVs which saves time. If they have pokerus, they get an extra double so if your pokemon has a brace and pokerus, they'll get 4x the EVs.
It probably sounds super complicated but just fight pokemon that give you the EVs you desire and your pokemon will be stronger because of it.
[Edited on 01.03.2013 10:56 AM PST]