How could a women have had been in a relationship before, had kids and all but still be a little shy when meeting new men?

It's sometimes hard to get back out into the dating world after you've been in a long relationship. Most people like this have spent years believing they'd never have to go looking for a parter again. So it's an intimidating thing.

That's normal. Even actors and singers who perform on stage still get nervous. You could also ask why do people who've held down jobs get nervous when attending new job interviews.