Here is how I typically approach it, I'm going to add some extra info that you're probably already aware, but hopefully it helps others when searching for issues since it is very difficult to find information about this software online.
For Aspen Flare System Analyzer, you model reducers using the "Connector" segment. You specify length or angle, although I have not found any difference in outputs regardless of how I specify the reducer. I don't usually worry about reducers for the Tees since the entrance loss in the branch is accounted for in the Tee.
If you're immediately expanding out of the PSV, you can do it two ways:
Either do a "Ghost Pipe", where you put a pipe segment in at the PSV outlet diameter and specify a length of 0, then add your reducer
Do as you said where you ignore the reducer, since Aspen will still calculate the expansion if the outlet flange and outlet pipe size do not match
For your case, since you have a valve on the outlet flange before expanding, you're going to want to do the "Ghost Pipe", where the length is 0, but then you want to add your valve in the Fittings tab. Then throw in your reducer and larger discharge pipe. If your simulation is having trouble converging, I find putting in a small length (i.e., 0.1 ft, 1 ft, etc) can help. This causes some trouble on PSVs with small outlet sizes (like conventional 1"x2" that immediately expands to 4") since the pressure drop is so large that any bit of pipe length specified at the smaller size can drastically increase the backpressure.
It should look something like PSV -> 6" Pipe (0 length, ball valve fitting) -> Connector -> 10" Pipe.
I highly recommend thoroughly reading the user manual, as painful as it may be. I have essentially read it front to back and have gotten a much better idea of how it operates. It's still missing plenty of info that I think it should include, but it provides a good foundation. The most critical part of it in my opinion is where it explains the different property methods and when to use them. For you or anyone else reading this, be careful with how you specify your methods and compositions. Check your "Calculation Settings" on the Home Ribbon, then click "Methods". If your VLE Method is not Compressible Gas, you must specify compositions using mole or mass fractions, not the binary molecular weight modelling.
Let me know if you have any more questions. I've only got a couple years of experience but have used Flarenet extensively and consider myself pretty knowledgeable on it.