While I don't currently have an iPod (waiting for Hugo to finish pimping the 4th Gen iPhone
) here are the apps I use (using wifi whenever required):
VNC (VNC Client)
Zenbe (Makes lists and allows you to sync them online)
UK Numbers (Convert areas to telephone area codes and vice versa)
Remote (Apple iTunes remote)
Air Sharing (File drop box over wifi)
eBay Stanza (eBook reader)
TC Calculator (Converts ordinary times to timecode and vice versa)
Moonlight Lite (Mahjong game)
Enigmo (Water-based puzzle game)
Days Until (Stick a date in and it tells how many days until the event)
Sound Box (Play sound effects on the device and also trigger remotely via a web page)
iDaft (Daft Punk in a box)
London Tube (Tube maps and route planner)
Tone Pad (Mini Tenori-on)
Amazon UKthetrainline (UK train times and journey planner)
The Stig (Nuff said)
Codec Calc (Data rate calculator)
Remote (Apple keynote remote, you too can be Steve Jobs!)
SpotifyFlickrSolitaireNow Playing (UK cinema listings)
Sonic 1 (Full game running on virtual Mega Drive/Genesis)
Convert Units (Convert between units)
Your Orange (Orange account status)
RAC Traffic (UK traffic status)
iPity (Mr. T based office productivity tool)
..and finally, not so much an app but a url:
http://iphone.tvcatchup.com/Almost as useful as iPlayer.