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Are you sure that you are putting in a blank disc? What happens when you put the disc inside the DVD writer? does it show up as a blank disc? This could be one of the reason for the multi session disc box getting greyed out.
A cd-rw would normally hold 500MB of data. A normal movie would need about 3-4 GB of data. You get programs that would save the movie on CD-RW as a VCD with compression to fit in lesser number of CDs. But you will not find many players that would play the cd-rw with the VCD format movie.
DVD-RW discs need to be formatted before use, similar to a Hard Drive. I am presuming you have not used this disc before.
Locate your DVD Drive in My Computer or Windows Explorer, right click the icon, then select Format. It will say "Format Completed" or similar, then it is ready to accept data that you wish to "burn" to it.