It's possible, yes, but I have never done it.
You can't use compression (ie tar.gz, tar.bz2, etc) with multivolume tar archives though.

I have no floppy disk here so this is a wild guess:

tar Mcvf /floppy/newarchive.tar *

This - I *think* - would create newarchive.tar on the floppy (if mounted on /floppy) with all files in the current directory, and hopefully pause and ask you for a new medium (disk) when it runs out of space.

hw