I desperately wanted to get my song "Last Day" on Grey's Anatomy because I thought it was just perfect for the show. So I researched who the music supervision company for the show was and discovered they had a blog. I read up on the blog and found that one of the music supervisors in the office wanted some Samoas Girl Scout cookies and couldn't find any. I quickly went out and bought some and sent her a package of Samoas (Carmel Delights) along with my CD and a handwritten note with my email address included.
I didn't follow up, SHE ACTUALLY CONTACTED ME and thanked me for the cookies and said she'd try to place a song. She hasn't, but I've developed a cordial email relationship and she always replies to my emails now.
The thing that surprised me most when really getting in deep with the business and networking, was that the gatekeepers to some of the most exclusive opportunities were actual people, with personalities, opinions, feelings, sweet tooths and bad hair days. This sounds like a given, but knowing this changes the way you approach them.
Do your research. If the person you want to contact has a blog - FOLLOW IT. Read up on the posts and get to know it well. Follow their Twitter and Facebook page - if it's a Page. Don't friend them just yet - too soon.
When you pitch them, if they see that you took the time to get to know them, maybe they'll return the gesture and listen to your song.
I receive a lot of requests from bands asking me for my opinion on their music and whatnot. They rarely start off by complementing me on my music or bring up something they like or respect about my project. They just want something right off the bat. I try to get back to everyone who contacts me, but I'm much more willing to respond much quicker if they start the email with a specific compliment or point of reference (like a mutual friend).
You can stalk them a little on Facebook without friending them and see who your mutual friends are and in your pitch email you could lead with that or get your mutual friend to make the introduction for you (that's best).
Either way, you need to open with a reason for them to take time with you.