As far as I know... FAT32 can't be larger than 32GB if you are planning to use it with Windows XP. An though with other OSs it can, it is usually not recomended because FAT32 is really old, and not meant for "modern" use (It cant handle files larger than 4GB, its way slower, it gets corrupted reall easy...)
My recomendation... If your not gonna rely on FAT32 for some heavy filelifting than yeah, go FAT32 and NFTS... and install the free version of NFTS 3G or something.
On networking:
When you connect your drive it will show both partitions as if they were independent drives... you will have two volumes mounted. This also applies to your local network: if you connect from another mac it will be as if 2 hdds were connected.
Upon ejecting any it will ask you if you want to eject the other, you can opt to or not (but of course, you can't safeley unplug the drive unless both are ejected).
That of course, if OSX has NFTS drivers installed. If not im pretty sure it will just detect one.