There is a great blog which can get you started here:
http://rubyonwindows.blogspot.co.uk/2007/03/automating-excel-with-ruby.html

The documentation for individual OLE methods will be in MSDN: 
http://msdn.microsoft.com/en-us/library/wss56bz7.aspx

The documentation for WIN32OLE is here:
http://ruby-doc.org/stdlib-1.9.3/libdoc/win32ole/rdoc/WIN32OLE.html

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