Basically, (as mentioned in another response) the docs that will get you anywhere are found on the Microsoft Developer Network. These are all geared toward Visual Basic, but you just need to translate them into perl (arrows instead of dots, for instance).
in reply to Can I use Win32::OLE to insert a TIFF in a Word document?
One gotcha occurs when you want to assign a value to a property. To get a proper lvalue for assignment, you need to enclose the property name in braces:
would be an example in Excel.