Have you created a Manual collection for overriding the PST tax on children’s clothing? You need to do this; it can’t be done with an automated collection. You go to Products, Collections, Create Collection.
Then you add all the children’s clothing to this manual collection. Each child’s clothing that is PST exempt will still also be in the automated collection as well as in the Manual collection.
Presuming you’ve already set up your GST/HST tax number in the taxes, you will then you create a product override under Settings, Taxes and Duties, Regional Tax Settings - select Canada, Product Override +Override, put in the name of the Manual Collection you made, select Ontario in the pull-down menu, and put in 5% for the tax.