I would stress the point that these were connection timeouts rather than command timeouts. In many cases the timeout occurred when calling SqlConnection.Open(), without even defining a command to execute.
What surprised me (I'm easily surprised) was that the timeouts were almost instantaneous - within 1-2 seconds. SQL Server connection strings include a parameter called "Connection Timeout", which I had not set, but the default is listed as 15 seconds.
I wasted a lot of time asking network nerds to trace the connection, check for dodgy switches etc, only to find a Microsoft blog post stating that in some circumstances the timeout applied will only be 8% of what is specified if your SQL server is mirrored:
http://msdnrss.thecoderblogs.
With this in mind I increased the timeout value in my connection string to 200, and the problem disappeared except at peak usage times.
I then added a "Min Pool Size" setting of 30, and the problem disappeared altogether.
Top hole!