For the future, you can definitely enable a new book within an existing campaign. Book access is controlled on individual characters, so you can tailor what books are enabled for each character. You can also set the default for all new characters within a campaign. And you can impose new settings on all existing npcs within a campaign. This is all accomplished via the Settings tab on the left when viewing your campaign.
With regards to these two problem characters, please open a support ticket and identify the problem characters (i.e. provide us with their ids or links to them). Then we can take a look at them specifically and see if we can figure out what the issue is.
I'll also ask one of our PF2 experts to take a look at this thread to see if they might have any interesting ideas about the source of the problem.
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