Create the additional files on the desired drives, and then you should identify the most utilised tables and split them accordingly.

You would simply change the storage for the clustered index, to move the actual table data to a new file.

Is there any reason you want to do this though?

Is I/O a problem or is there an issue with the overall amount of diskspace required for the Database?

EDIT: Not sure if it is possible to do exactly what you're looking to for in your explanation above - you are basically wanting to exactly split the I/O across the 5 drives?

Ultimately you're looking to RAID.