Marvel Unlimited may lack some books but for the most part is quite robust in terms of selection. You should be able to find all but the newest series I think.
Sites like the below have extensive reading orders. They even specifically recommend books for MU subscribers.
https://www.comicbookherald.com/blac...reading-order/
Since that’s pretty long and will include a lot of filler, I would recommend this volume:
https://comixology.com/Marvel-Knight...l-comic/703774
And this one:
https://www.comixology.com/Black-Wid...RlZEVkaXRpb25z
And some Daredevil/Black Widow action:
https://www.comixology.com/Daredevil...RlZEVkaXRpb25z
You may find some of the collected volumes are missing in MU, so you may have to look up the issues individually.
From time to time when I’m trying to figure out what to read I’ll just google “must read black widow stories Reddit” and it produces decent results.