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In theory that will work, but remember to do a few things first. Make sure you do a complete copy of all files including hidden files. Also remember to mount and unmount the card cleanly on the PC or you might get some files that are tagged as in use and won't let android access them properly. Finally, when you put the new sd card in the phone and restart, give it a few minutes to rediscover all your files before you try to use them.
One other note is that if you had any media files that you used as ringtones or notification tones, this might break the association and you'll have to reset them.
As long as you copy (not move) the files from the old sd card, you can always put it back to restore your phone if something is amiss with the new card.