Make sure the secondary usergroup is set to Not Set, or No. If a permission is set to Never, then the user will Never have permission regardless of any other usergroups. This is by design, because it is semantic with the implications of the word "Never", and it is consistent with the design of the "Never" level that is native to XenForo. This choice is available to vBulletin users because there is no reason not to make it available in both (in fact there would actually have been more development work required to remove it for vBulletin).
However, if the user is granted permission in a primary usergroup globally, and revoked that permission in a different usergroup only for a specific area, and the primary usergroup is not also customized for the same area, then there might be a bug where the custom permissions for a different group are overriding the global permissions when viewing that specific area. By design, custom permissions should only override global permissions for the same usergroup. If there is such a bug, I don't see a way that it would affect wiki functions that only rely on global permissions (like special pages).
Let me also stress that it doesn't matter whether the user has a group as its primary group or as a secondary group. A primary group doesn't override a secondary group. In vBulletin, all groups are given the same weight when it comes to permissions.
If the primary usergroup is the wiki moderators group, the user will not get permissions from this group, except for areas where the user has been designated as a moderator in the Permissions > Moderators panel. Thus, simply adding users to this group will not give them permissions. You must actually define them as a moderator. This is by design.
If the user has a user mask in Permissions > Access Masks, this will completely override their permissions from all of their user groups, except for settings with a "Not Set" value. In the case of "Not Set", it will defer to the calculated permissions based on the user's primary and secondary groups and the current area being viewed. This is by design.