Are you possibly using XNA Game Launcher on the Xbox 360? There are two downloads available on Marketplace, and that one is for XNA Game Studio Express 1.0.
For XNA Game Studio 2.0, go to Marketplace and download XNA Game Studio Connect. Besides the difference in title, the new XNA Game Studio Connect will display the connection key directly on the Connect to Computer screen instead of in a slide-out panel that disappears before you can test the connection.
If you are running the correct application on the Xbox 360, then changes in your firewall settings or router or wireless network connection could be causing problems.
To ensure that you are at least on the same subnet, try intentionally entering an invalid key when trying to connect. If the Xbox 360 can "hear" your PC, you will see a message on the TV screen saying that an invalid connection request was rejected (and it should show your PC's IP address). If you don't see that, then something is blocking the UDP broadcast packet from your PC.