I took 3 Vueling flights this week, LGW-OVD, OVD-BCN and BCN-LHR. I booked direct with Vueling and chose the option including a checked bag and some limited seat selection. I was able to select the Emergency Exit row on each of the flights.

The EE row has very good leg room, I'm sure better than BA, for some reason I'd assumed it would be determined by regulation, but I guess not. Selection of the EE means you don't have to have your bag in your foot space, although I'm guessing it doesn't mean you can put a larger bag in the over heads, as bag size is enforced at the gate.
Boarding of the 3 groups was efficient, with the bulk of people in G3 as was I. The gate staff were enforcing the groups, certainly at LGW and OVD, I didn't see anyone at BCN try.
Hand Baggage was enforced properly, as only a small under seat bag is allowed unless you've booked the overhead. Removing the overhead bin anxiety removes the need to board at early.
As an aside Vueling don't let you use headphones of any sort for take off and landing if you're in the EE rows, which seems reasonable.

I didn't miss the BA thimble of water or the biscuits, and really I'd give the overall experience as a win to Vueling. I could maybe do something in settings, but the most annoying part of VY was the email pressure to upsell.

A very small sample set, but it certainly means I wouldn't hesitate to use VY again. Economy travel is not great, so I'm not trying to promote VY here, but it's certainly no worse than BA.