Whoa, I think I figured it out!

To scrobble from iPod Touch to Last.fm through iTunes:

• * Connect your iPod Touch to your computer.
• * Open iTunes (if it doesn’t open automatically).
• * When iTunes recognizes your iPod, click “iPod Touch” (under “Devices” on the left sidebar).
• * When that loads, click the “Sync” button at the bottom right of iTunes.  Yes, you have to sync first! (Doh!)
• * THEN when that process is complete, open Last.fm.  You should already have your iPod configured in the application.  You can find tutorials for that.
• * In the taskbar, click Help > Diagnostics.  Click the tab “iPod Scrobbling” and make sure your settings are correct.  Click the “Scrobble iPod” button and watch it do its magic.
• * After a minute or two, it will open a pop-up window that asks you which tracks you want to scrobble.  I generally will leave all of them and then click “Scrobble.”  Sweet.

The tricky part: realizing that I had to sync FIRST before scrobbling from the desktop app.  I still cannot figure out, besides using Simplify Media, how to scrobble directly from the damn iPod Touch through a wi-fi connection.  Someone enlighten me?  KThx!