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I've got a DX58SO with 6 gigabytes triple-booted with Vista 32, Win7-32, Win7-64, all on a RAID 1 (mirror).
Yes, it's true that under a 32-bit OS, only about 3 and a half of your 8 gigabytes of RAM will be used.
I've found multi-boot to be straightforward. Presumably you know how to divide your disk into volumes, and install the new OS on a separate volume. So, other than the fact that each OS can access the volume on which the other is stored, they're pretty much independent of each other.
Since the RAID you're adding is only for data and not for the OS, it should be pretty safe any way you do it. You'll just add the drives and then go into BIOS to tell it the RAID configuration. Then, for each OS, you'll install the Intel Rapid Storage Technology management program.
Once you get a 64-bit OS set up, you might want to start installing all of your software on it, with the goal of eventually making it your exclusive OS. Unless something cannot be ported, you'd probably rather be running everything under 64 bits if you can.