I'm afraid there are a few steps to this. What you need to do is:
1) partition the new card - choose whatever size ext4 partition you need when you do this.
2) with your current card in the phone, take a nandroid backup
3) copy the entire fat32 partition of the current card to your computer (make sure you get "hidden" files and folders too, i.e. those whose names start with ".")
4) swap cards and copy the contents of the current card to the new one. Probably simplest to do this with a card reader or with the phone in recovery mode and the card mounted (mounts and storage menu in recovery)
5) restore the nandroid backup
The reason for all of these steps is that most computers can't see the ext4 partition at all, so you cannot simply copy the contents of that to the new card. However, the nandroid will back up the ext partition, and the nandroid backup lives on the fat32 partition. So if you take a nandroid with the old card, copy everything to the new card, put the new card in the phone then restore the nandroid that will fill the ext partition on the new card.
P.S. Why is it obvious that you want to make the ext4 partition larger? If you are short of space on it, yes, but you don't need to scale it to the card. Unless you are using a ROM that requires it I'd not make it larger than 1GB just for app storage.