I had the same exact issue using VS2013 Ultimate SP2.
It seems that this only works when it is a Silverlight project, but as soon as you open Blend for Visual Studio, you can go to File -> Open Project/Solution... and select the project you want to create using Blend.
As far as I know, this is the only way to open Blend without looking at VS 2012/2013 program folders. I tried it several times with WPF (even by right-clicking on certain XAML files) without success.
Perhaps this has been fixed, so I will update VS2013 to the latest version (SP3) and update this answer with my findings.
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