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In order to create a new Volume Group you'll need to create new Physical Volumes, so it seems what you want to do is to resize the existing Physical Volume/partition (which would also reduce the amount of storage space in the associated VG), not shrink the VG (which involves removing Physical Volumes).
The size of a Volume Group is determined by the combined size of the participating Physical Volumes. You can only directly reduce the size of a Volume Group by removing Physical Volumes; there's no way to instruct LVM to use, say, only half of a Physical Volume in a Volume Group.
However, provided there's unallocated space in the Volume Group, you should be able to run pvresize on the existing Physical Volume. Yes, you can do that on an Physical Volume while it's a member of an active Volume Group. Once the Physical Volume has been resized, the partition on which it resides can be shrunk accordingly.
Another alternative would be to add a temporary Physical Volume to the Volume Group, and then remove the current Physical Volume, delete and recreate the partition and Physical Volume, add it back, and finally remove the temporary Physical Volume.
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