Exchange ought to work ok, but you don't need it if you aren't using push. I prefer fetch, but to each his own on that.
Now back to the groups...LOL.
You have a few ways that you can do this.
1) I am familiar with Outlook, and Outlook supports both groups and new folders in contacts. If your PC mail client doesn't support that, then you will have to split the contacts elsewhere.
2) Open a Gmail account and sync one set of contacts there, and the other on the computer. You don't have to use Gmail for mail. If you prefer to keep using Hotmail, you can just use it for contacts.
2b)If it were me, I would open two separate Gmail accounts, and use Gmail instead of Hotmail, since Gmail supports contacts, calendars, voice, and a lot of other neat stuff. Plus, it works very well with the iPhone. You could always forward your Hotmail mail to your Gmail account, and you could delete it off the phones.
3) Same thing with Yahoo, though I much prefer Gmail.
4) Open a MibileMe account. I don't recommend this if you are just wanting a place to sync contacts. You can read about mobileme here http://www.apple.com/mobileme/
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