Based on what I know about Redis, I'm guessing it will be
significantly faster than using SQL Server - is that a fair
assumption?
It will be faster than SQL Server since it's optimized for in-memory based operations, however its speed isn't the only advantage. Support of advanced data structures offers a great deal of flexibility when dealing with various scenarios.
If so, how does the Windows version of Redis implement fail-over?
There is a link in download section to unofficial windows based port of redis which however isn't meant to be used for production purpose. Official version of redis supports replication and sentinel has automatic failover, but it's hard to say what's the state of these features in windows port. In general I wouldn't recommend to use redis on windows machine but rather use virtual machine with linux distro and run it there.