iPhone/Android/BlackBerry: When you're driving or traveling, that's when you don't want to wait on hold or talk to an automated phone system. The Dial Zero mobile app has a database of buttons and phrases that will cut to the chase.
There are online databases, like GetHuman, and even apps like previously mentioned Fonolo that promise to patch you right into where you want to be in a customer service tree. Dial Zero is a less complicated mobile app that has a database of more than 600 companies and the buttons to hit, or phrases to say, that gets you to a real customer service representative right from the get go. Explore around, and you'll be amazed at the vast variety of schemes and phrases in place: hit 0, hit 7, say "Speak to someone," or try to say "I need help," without sounding too desperate.
Dial Zero is a free download for iPhone, Android, and BlackBerry phones.