Here's my workflow (from an abundance of caution) and going from memory, so I could have missed a step or the order:
Level and check balance of the mount (8 of 10 root cause for my bad guiding is from being out-of-balance in both RA/DEC)
Polar align (I'm still old school and use QHY PoleMaster but learning how to PA with ASIair)
I've got the GPS unit, so I confirm the Lat/Long & time on HC
Perform a 1 star alignment (usually Chab or some other stars in minor)
Check to make sure you've got the right focal lengths for each scope
Power up ASIair (I have found that the AVX seems never to connect on the first power up - I disconnect the AVX, reopen, then close and restart the iPad app, and the mount connects with the GPS
Check the focus quality of the guide (ASI120MM-S) and imaging scopes (William Optics 81 with ASI071/ASI183/ASI1600)
Slew to a good star field location (perhaps close to your target)
Take a preview image, adjust focus as needed
Take a preview image
Execute Plate Solve
Sync to mount (I usually have connect to SkySafari Pro and check to see if the target has been captured)
From ASIair, I select my target, then execute a GoTo function
Once on target, do another plate solve and Sync & GoTo target, check if centered in Preview
Select Guide, select star, star calibrate and start guiding - will adjust agressiveness in the 5-10% range, let settle, and see if there's improvement (usually can get in the RMS range of 0.75 to 1.0 and can easily get round stars with exposures in the 200 - 600 range if I stay away from the scope that's on my driveway and there's no breeze)
Check and confirm how you want the image file names, including the image name; check that you've got the cooling settings on too
Recheck all of image settings (including if I've got enough space on the SD card and duration of session to make sure my target doesn't move behind a tree or my roof line) - I've found sometimes things change - not sure if it's me or the application - but I always confirm bin settings, exposure and count to make sure I'm not surprised at the end of the night (alas, in my last session, somehow had all bin's set at 4 rather than 1 - what a waste)
Still learning and experimenting with the right combination of settings for dithering
Periodically check the captured images (the first few and then periodically thereafter) to see if everything is working and playing nicely
If everything works, then do any flats, bias, dark frames
Hope this helps...
And if there are better ways, steps or an order that should be considered, would welcome the feedback.
Jim