I use Macs and PCs (Win XP Pro) extensively at work. In my experience, I've found that the PCs can see the Mac shares more reliably than the other way around.
On the Mac, I use Sharepoints which makes it a lot easier to share specific folders or complete volumes:
http://hornware.com/sharepoints/
On the PCs, I run into all sorts of problems where one won't see the other even though it worked fine the day before, yet a different PC will see the share fine. One thing I found when on the Mac trying to access a PC share was it wouldn't work because I had changed the XP user name at some point in the past. Using the current user name just hit a brick wall so I had to use the original name, as found in C : Documents and Settings.
If you want a Mac to connect to the PC everytime you log in, type the following in Script Editor, replacing the relevant info:
tell application "Finder"
mount volume "smb://domain;username:password@IPaddress/sharename"
end tell
Then Save As, format=Application, untick Startup Screen and save this somewhere suitable. Then go to System Preferences->Accounts and add this newly-created application to your login items.
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