You may want to consider PC BSD .. this is a desktop version of FreeBSD ... there are various threads/wiki entries at the PC BSD site on how to install in a dual-boot with Windows XP. From here you can read through the FreeBSD Handbook at freebsd.org to learn about the core system.
Depending on what you are wanting to do to "learn networking" you may need to eventually acquire a second computer to umm, setup a network and get a better feel for how network protocols work, test firewall settings, etc. If you get to this point, I'd probably recommend using the default install and learn how to configure the entire system from a base install, from the shell. It will take time to get use to working at the shell, but if you have plans on getting into the field (or have plans to extensively use BSD systems for day-to-day tasks), learning the power of the shell is worth the time.
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