UKH

just bought a new pair and in a rush thought, yep there good. 
now I find that on one toe only, they are uncomfortable, in fact hurt.
getting them in the morning before feet had expanded wasn’t a good idea, let alone trying them immediately on a Boulder problem so I can’t return them . 

Is there anyway of stretching the big toe out a bit without wearing them. 

Just wear them for a while whilst watching the telly or something. They should stretch out a bit or at least mould to your feet. My current shoes (5.10 Anasazi) were painful for a short while, now I can wear them all day long, in fact most of my shoes have been like that.

That’s like spending an evening with the mrs, painful 🤣🤣 I’ve used 2 different brands til now and they just fit. 
oh well, no pain no gain 😩

Of they're leather you could try aoaking them in warm - tepid water and then climbing in them, worked a treat for my Miura VS. I've also put shoes one and used a hair dryer to heat up painful spots then let them cool whilst still wearing them, it worked to an extent but wasn't a miracle cure. Careful not to cause delamination by getting them too hot though.

Try wearing them with a plastic bag on each foot.  You can wear them at home, or better, do a couple routes.  Then try them without,  they'll already be stretched a bit and should make life a lot easier 

Try wearing them in the bath, then dry them out slowly, periodically putting them on for a few mins as they dry (if they dry too fast, like on a hot radiator, they can go hard and be worse). 

At home, wear thin socks + plastic bags + watch TV until in agony. Repeat. Next day, try without socks. If still terrible, sell them. If almost OK then run over the front half of the shoes (carefully) with front wheels of car. It may destroy the shoe but it’s always worked for me.

Saw this video on breaking in new climbing shoes, I haven’t tried any of them but have had success with shoe stretchers:

https://www.epictv.com/media/series-home/climbing-daily/230997?episode=6083...

< If almost OK then run over the front half of the shoes (carefully) with front wheels of car. >

Just checking: do you need somebody else to drive the car, or do you take the shoes off for this procedure?

Wear them round the house. Plastic bags on feet can help. 

In addition to the meeting/drying methods people have listed, you can also freeze them. Fill you shoes with bags of water, and bung them in the freezer overnight.

If all else fails and you don't want to /can't sell them a couple of cuts in the rubber can relieve pressure points.