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Hi Tobiashagge,To know about the list of supported ContentTypes available, please refer below link.https://developer.salesforce.com/docs/atlas.en-us.pages.meta/pages/pages_compref_page.htm I think .xlsx will work if cache = true in visual force page like below.
Please refer below links for more information.http://blog.shivanathd.com/2013/03/visualforce-to-excel.html http://salesforce.stackexchange.com/questions/55958/when-i-change-a-visualforce-page-contenttype-can-i-somehow-give-it-a-file-exten Hope this helps you!Please accept my solution as Best Answer if my reply was helpful. It will make it available for other as the proper solution. If you felt I went above and beyond, you can give me kudos. Thanks and Regards<apex:page standardController="Account" contentType="application/vnd.ms-excel" cache="true">
Sandhya