Account attributes are considered to either be initial attributes or capability attributes. Right-clicking on a Provisioning User and selecting to "Sync Account Attribute With Templates" will only consider the capability attributes so this will not perform the operation against all attributes.
The other approach is to reset the Provisioning User value to its current value and choosing to sync at the same time. This cannot be done via the Provisioning Manager however as the Provisioning Manager would realize that the new value is the same as the existing value. You can however use etautil to set the Provisioning User attribute value to the same existing value and in the same operation include the eTSyncAccounts=1 flag in order to propagate the change to associated accounts based on the templates.
With respect to the IM (Identity Manager) User and Provisioning User, there is no "sync now" task for that, but executing an IM task which has AccountSynchronization=OnTaskCompletion will result in IM comparing the userstore user with the provisioning user with respected to the IME mapped attributes and where the values differ IM will send to the Provisioning Server the current IM userstore values for those attributes.