i have personally successfully used multiple 4tb hard drives with my raspberry pi and see no reason why your 5tb and 3th drives would not be compatible with the pi simultaneously. The only potential problem that i can see arising would be that Fat32 is a file system that is limited to partitions that are 2tb in size, so formating a 5tb drive to fat32 may require 3 partitions, which is likely the reason that your windows pc is not recognizing the drive as being 5tb in size. you can read more about this phenomenon here
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