Any new HDD must have two operations performed before you can actually use it - and often they are "bundled" into what looks like one step. They are: Create a Primary Partition that is bootable; and, Format that Partition. If you Install a Windows OS, these two steps will be done for you before the actual Install process begins. If you clone from an old drive to a new one they also will be done. BUT some of the clone software I've used defaults to making the cloned Partition on the new drive the SAME SIZE as the one on the old drive, even though the new drive is much bigger. You CAN change that by using their menu systems, but that is the default.
You don't tell us how you "installed it, got everything back up and running and what not." Did you clone from your old drive to the new one? Did you do a fresh Install? Did you have a full backup you used to restore to the new unit?
Whatever the process was, it appears that it Created on your new drive a Primary Partition of only 100 GB or so. This means that the rest of your new HDD is still there and empty. It is called "Unallocated Space" on that HDD.
Before going any further, let's check one thing. Older computers from around 2000 sometimes can NOT use an HDD over 137 GB if it is an IDE type. But this does NOT apply to any SATA drive, so if your new unit is SATA, don't worry about your hardware. IF your new unit is IDE, though, you'll need to check whether your machine can use a drive this large. First clue: what was the size of your old drive? If it was over 128 GB in Windows' way of counting (137 GB according to the HDD maker), your machine CAN use such large drives, so don't worry.
NEXT, however, is your OS. Windows XP in the original version could NOT use such large drives. The thing required (Support for "48-bit LBA") was added in SP1 and has been part of all subsequent Windows. So, IF you are now using the old original version of Win XP, you need to make some changes. Otherwise, forget this, too.
Once the questions of machine ability and Windows version are settled and you are sure you CAN use a disk of this size, you have three options from where you are.
1. Start over again. Make SURE you have all your stuff backed up someplace else. Then Delete the existing Partition and Create a new one that is the full size of the 640 GB unit, then Format it. NOW you re-Install the OS and all your apps and restore your data. IF you are Installing from a Windows CD, its early menus will let you choose the Delete the old Partition and Create a new one and set its size. On the other hand, if you are re-cloning from your old HDD (assuming it is still limping along), make sure you find out how to set up the cloning software to set the size the way you want.
2. Don't worry about all that. Leave the 100 GB Partition in place and use it as your boot "drive". (Any Partition is treated by Windows as a separate "drive" with its own letter name, even if it is actually on the same HDD unit as another "drive".) Use Windows' built-in tool Disk Management to Create another Primary Partition (you can have up to 4 on one HDD) from the Unallocated Space, and use it as a second drive where you store all the data. You will probably want to change Windows' defaults about where it stores data, and you may want to re-Install some of your app software on the new "drive" to avoid filling up the first one of 100 GB.
3. Buy and use a utility like Partition Magic which can Extend the existing Partition into the Unallocated Space, effectively adding as much as you like (probably all of it) to your existing C: drive. Windows itself will not do this job on a boot Partition, but several third-party utilities will.
Post what you situation is and how you got here, and what progress you make. If you need more help, we can advise.