When you see or know someone you really like, it's important to at least know if they're already dating before you actually hit on them, or ask them to dates. It's a real turn-off when they have to tell you that they're already with someone else, so it's best to get some information before asking such a question.

You're probably reading this Wikihow before you actually ask or even think of it. So you're probably lucky. If you've had experience, here are some extra pointers in case you did something wrong, or want to add more to your methods.

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[edit] Steps

Grab Some Spine! If you lack confidence, you'll never get to ask the question. If you really need it, just take a breather and go up to the person of your fancy.
Be Polite! Be sure to be polite to a person when asking this. It's a personal question and they need your utmost respect, especially with a person you barely know. (See Warnings)
Get On With It! They haven't got all day! Just ask them in a nice manner, "Excuse me, are you single?", just avoid being blunt about it. They may laugh. (See warnings)
Don't Let "No" Get To You! If they are dating, or not telling, they have every right not to tell you and have every right to date whom they want. (See Tips AND Warnings). There are more fish in the sea.
If "Yes", Get To Know Them! You got lucky! Ask them for telephone numbers, e-mail addresses, other forms of communications! Build a relationship, it will turn into a friendship, and maybe you might start dating! (By the way, see a warning regarding this, also)

[edit] Tips

Be yourself! Be yourself, be yourself, be yourself...
It's best to introduce yourself beforehand. Make sure this person at least knows your name, so that she at least knows a little about you. This is how almost all friendships start.
If you don't have enough confidence, you could maybe read a little more on how to build confidence! See Related Wikihows if you need assistance in that area.
If you're not good at being polite, you'd better start! Polite people DO get more friends. It is a fact.
It's a relationship! Don't be super serious about it! Make them laugh! Make them smile! They'll like you more!
It's just a question. You don't betray anyone or anything when you ask it. Even if you feel wrong about doing it, it's just fine. It's totally normal. Chill!

[edit] Warnings

DO NOT BE ANNOYING OR RUDE! Ultimate No-no! Don't even think about saying inappropriate comments to strangers! You will have a hard time in life acting that way. Much less build a relationship.
Never persist to convince them to date you instead. This is also a no-no! They can date whomever they wish. You can find lots of people like your "soul mate". Avoid obsessing over them, avoid flirting inappropriately, do not persist to ask them about their love life! If they say "No", you are done! No is no, no matter what you think. This is forwarded especially to guys!
If you get lucky enough to get a Yes, that's great! However, do not get super hyper and excited. That makes you look weird and slightly annoying to be with, thus breaking that first rule. Avoid calling them too much, and avoid sending them hundreds of messages. They're your "soul mate" but don't overdo it!
Watch your sense of humor. It's fine to be funny, but if you get mouthy and they don't like it, STOP and apologize. Continue to get to know them. Without overdoing it, of course.