I am building a new rig and am going to have a 256GB SSD for the OS and programs and use a 750GB HDD for storage and such. So my question is if I copy all of my pictures and documents and music from my old computers hard drive to the new HDD, after I install it in the new build along with the SSD will the pictures be accessible by just simply clicking on My Pictures and documents by clicking on My documents?
yep, but you will have to add the hard drive directory to your default library.
or create a NTFS junction point to graft in your hard drive into a subfolder of your SSD
or use the disk manager tools to mount your HDD into your photo folder.