As a general rule, most of the major motherboard manufacturers like Asus, Abit, and MSI have 64bit drivers for their MB chipsets, and for built-in MB devices like audio, NIC, 1394 controllers, and USB controllers.
If the the MB manufacturer doesn't have 64bit drivers, Nvidia, ATI, and Via will certainly have 64bit drivers for all of their chipsets. Moreover, C-media and Realtek have 64bit drivers for their primary audio chipsets found on many MBs.
64-bit drivers for some of the more popular printer models come with the Winx64 installation CD. Just make sure that your printer is connected and powered on when you are installing the OS. If the Winx64 CD has proper printer drivers, they will get installed like other devices.
As for other hardware, check these two sources:
AMD's Big List of 64bit drivers
3DVelocity's 64bit Hardware Compatibility List
Between these two sites, you should be able to determine whether your preferred hardware devices have 64bit drivers. Of course, you could check the individual device manufacturer's websites because they release new 64bit drivers all the time. For example, Epson just put up 64bit drivers for my new Aculaser CX11NF color laser multifunction printer.
As for software, almost all major 32bit applications can run in Winx64, including pc games. In fact, my 32bit pc games run as well as or better in Winx64 as in WinXP. For example, Far Cry 32bit runs just as fast under Win x64 than under Win XP Pro in my dual-boot system. Of course, Far Cry 64bit is nice, too.
I'd guess that Win x64 is backwards compatible with 90% of all 32bit software.