Sure, this is possible. It would work something like this:
1. Do the install with the single drive
2. Note the device node for the single drive (probably /dev/sda or /dev/hda) and whether any RAID arrays exist (/dev/mdX)
3. Attach the two RAID drives (unformatted) and note their device nodes (possibly /dev/sdb,c or /dev/hdb,c -- but could vary)
4. Use mdadm to create the new array /dev/mdX comprised of the two new device nodes /dev/xxx and /dev/yyy
5. Use mkfs.ext3 to format the newly created array /dev/mdX
6. Create the desired mount point - if needed
6. Edit /etc/fstab to allow SME Server to automount the new raid array (/dev/mdX) on whatever mount point you want