Ensure that the target card (the new one) is formatted as FAT32. Because it's only 32GB, it should probably be easily formatted as FAT32 by Windows itself if it isn't already FAT32.
Once it's properly formatted, copy everything from the source SD card (the old 4GB one) to the target SD card. (the new one)
Once that's finished, insert the new card and ensure that your 3DS still powers on and can play the games that are on the SD card.