If you want to completely minimize the risk of her suspecting you're buying a ring, you can get a rough idea just by holding her hand and trying to remember how it feels. Then compare that sense impression against your sister, mother, friends, your own fingers (pinky, perhaps?) and those of the ring salesperson.
Err on the size of being too big. If she says yes, at least you won't draw blood cramming it onto her finger. Then get it resized as necessary. If all else fails she can wear it on a chain around her neck until it's resized. Maybe you should carry a chain in your pocket when you propose, just in case?
As pointed out in one of the comments, completely surprising her with the whole idea of getting married (rather than just the circumstances of when you'll ask) is not necessarily as good an idea as our romantic-fiction-driven ideals would lead us to believe. Make sure you and she are on the same page about marriage, without necessarily making her certain whether/when you will propose.
Also, if her parents are at all present/important in her life, make the effort to get their blessing before you propose. Their refusal won't make anything worse than it would end up being anyway, whereas their blessing will make everything much happier for all.
Oh and one final note, having read one of the previous answers. If you surprise her a little, and you make it romantic, and you offer to devote the rest of your life to her, and while offering her a diamond ring to seal all of this you explain the very reasonable fact that you didn't know her ring size so it might be a little too big---if after all of that she looks at the size and scowls and says "oh, so you think I'm that fat??"---then, my friend, this is what you do: marry someone else.