I think you just need to understand the enterprise structure.
You have said "32 segments which they consider as each Cost center(Segments) and also 5 segments they maintain storage location."
As we know cost center is not comes under enterprise structure. So you have to maintain this as Purchase Org. or Plant and its depend on your business procurement process.
Purchase organization is used for differentiate the enterprise according to the purchasing.
Plant is used to differentiate the enterprise according to procurement.
How your 32 segments are used in your organization?
Its purchasing will different for all 32 segments (use 32 purchase organization) or in just one purchasing you have different unit for procurement (use 32 plant).
Regards