Note: I've left my original content below; feel free to remove it if that is the preferred way to post answers.
Initially I could not find a clear source for the namespace
http://schemas.openxmlformats.org/spreadsheetml/2006/main.
I found that http://purl.oclc.org/ooxml/spreadsheetml/main is used in the ISO/IEC 29500-1 and ECMA-376 documents.
When I was looking through the files in zip 'ECMA-376, Fourth Edition, Part 1 - Fundamentals And Markup Language Reference.zip' I noticed there are two sets of XML schema files:
OfficeOpenXML-XMLSchema-Strict (In Part 1)
OfficeOpenXML-XMLSchema-Transitional (In Part 4)
I found that the Strict schema uses the purl.oclc.org namespace while the transitional schema uses the schemas.openxmlformats.org. Both sets contain the sml.xsd file (Defines SpreadsheetML) but with some differences. It seems that the different version of MS Office support different verisons of the standards (found on http://en.wikipedia.org/wiki/Office_Open_XML).
Original answer:
It appears that the comment by JasonPlutext is correct. I downloaded the file 'ECMA-376, Fourth Edition, Part 1 - Fundamentals And Markup Language Reference.zip' from the ECMA site which contains the file 'OfficeOpenXML-XMLSchema-Strict.zip' which then contains the file 'sml.xsd'.
I searched for the namespace you're looking for and found this website that appears to be an online version of the schema using the same namespace. I checked a few elements and they all appear in the sml.xsd file.
What is odd is that that none of the files in the downloaded schemas contain the schemas.openxmlformats.org namespace they all contain namespaces like this one
http://purl.oclc.org/ooxml/spreadsheetml/main
you can navigate to this URL in a browser and it references the ISO standard ISO/IEC 29500-1. I'd say they refer to the same thing but the purl version is less specific compared to the schemas.openxmlformats.org version.