This should index fine across the block on all of the chainrings – even crossed over right at the limits (50/32 & 22/11 or whatever you have), although as you’ve already said – you won’t really want to be riding it very far on ratio’s like that …
Like Boriselbrus there ^ – I’d [also] suggest checking the alignment of the front cage too; actually, do that first, then …
Make sure that the rear cage isn’t bent / twisted / can cope with the range of gearing / has the H/L screws set properly, and that your hanger isn’t too far out of alignment, then …
Drop the chain onto the middle ring on the front, and then set up the indexing on the back. Cable tension will be quite critical – on a 10 you aren’t moving much with each click, so <1/16th of a turn might be enough to knock it out.
Double check that the new cable has fully located into the lever too – I’ve wasted ages in the past hunting for a random indexing failure when bike building, only to find it was down to the cable not quite being settled in place … 🙄