4 and 5. I would go 5, since the rewards are better.
Who are the best champions to bring? I can upgrade some if they're not high level enough
SS, Starky and BWCV for v5. SS can do V4 Electro. Starky can do DPXF. Look up V4 DPXF heavy span and you can fnd out the start
Also, variant 4 dpxf can be a bit iffy with starky. If you decide to go for heavy spam, his taunt can make him throw his special when you're spamming (which equals instant death). If you decide to play normally, mighty charge is a thing.
Go for variant 5 completion first. Sym supreme, Black Widow CV and Stark Spidey are great there. You can use the r3 gems from the first 2 chapters to upgrade Carnage, he is great for chapter 3. And maybe even Spidergwen. See how easy it goes, then either start exploring V5, but you would probably be better of using your new r5 to do v4, since only 2 missions require 5 stars and the rest are lower.
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Domino(medium light then back off)/havok(medium medium then back off) for electro boss v4
Havok is the best option for that fight.
If you decide to play normally, mighty charge is a thing.
Sym supreme, Black Widow CV and Stark Spidey are great there.
You can use the r3 gems from the first 2 chapters to upgrade Carnage, he is great for chapter 3.
And maybe even Spidergwen.
See how easy it goes, then either start exploring V5, but you would probably be better of using your new r5 to do v4, since only 2 missions require 5 stars and the rest are lower.