LeviM,
The answer to the question: "can I rotate an Eccentric reducer at an angle?" is Yes! you can install an eccentric reducer at any angle required by your configuration.
That being said there are other basic piping rules that need to be considered. One basic rule has to do with "Pockets".. It appears that the configuration you are showing has a pocket in the bottom of the 20" elbow and the low point on the eccentric reducer. This is not good no matter what the commodity is. If it is mandatory that you have this low point then you will need to add a low point drain for hydro testing and if this service is Steam you should have a Steam Trap.
The other basic rule has to do with what dictates. The Caesar program does not dictate the design or the piping configuration. Caesar is an analysis tool to check the Stress related issues of a Design. Just because Caesar cannot or does not show a "rolled" Eccentric Reducer does not mean that the piping configuration cannot have a rolled reducer.
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Jop