The faster the boot drive, the faster the system will boot and theoretically run.
It's best if boot drive is physically different from applications, documents and scratch (virtual memory) disks. An optimal (speed-wise) system would have separate drives (and possibly separate controllers) for each of these. In this case System, applications, documents and virtual memory could all be accessed simultaneously (or as good as, no time wasted moving the disk heads). However in day to day use, this is overkill 😉
I do recommend a separate scratch disk for photoshop if you have one spare. The speed increase for large files is noticeable even on my G3 iBook 😎