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You can find lost of information on printing and samba by googling but to get you started there are actually two parts, the samba client and server. The server sets up printer and file sharing so windows can talk to linux PCs. The client lets linux PCs talk to windows PCs. smb.conf is just for the server so it does not matter if you are just using the default setup. Many file browsers etc have the samba client "built in" like Nautilus which is why you can see windows shares when you type smb://
What is the make/model of your printer? You can add a printer via CentOS printer configuration tool or through cups web configuration pages (http://localhost:631
). FYI cups is the print server.