Let's see if I can help with this. The versions of PalmOne software have changed and I am not always caught up. (I don't think I installed my Centro software on any of my PCs yet)
Start > Programs > palmOne - There may be a program to change the HotSync conduit. It might also be something other than palmOne, but that's what the program folder is on the last version that I installed.
When you brought up your Palm Desktop, was there any information in it? If there was, was it the most recent information from your Treo? That would be a good clue as to what's happening.
On your Centro, there are many ways to establish a connection to a Palm Desktop / Outlook data source - Modem, Cradle, Infrared, LAN... Since you use your sync cable, the Cable/Cradle connection is the only one you really need to be concerned with.
Finally, if you're only syncing with the local Outlook on your PC, make sure your Outlook is open before you start syncing. (sometimes, to solve sync problems, I've actually uninstalled and reinstalled the palmOne software to make it work properly and that's a common solution in the Treo community)