I'd first introduce myself to Twilight.
"Hello, I'm Sterling Silver. I'm new here, but I saw you when I was in Canterlot for your coronation. You must have exquisite knowledge of magic! If it's not a problem with you, um, can I see some of the books you use? or maybe you could teach me some?"
after that, I'd probably ask about pinkie, as long as pinkie didn't find me before i met twilight. if she did meet me, it would probably be something like this:
"HI THERE, YOU'RE NEW! I'M PINKIE PIE, YOUR NEW BEST FRIEND!!!" giant hug
catches breath hello! um, yes, i'm new here. glad to have gotten a new friend already. wait a sec, you were with twilight at the coronation! you're obviously wonderful friends of each other, so do you think i could meet the rest of em?
the above would be said so long as i was able to speak without her interrupting.