I don't use smb4K-- LinNeighborhood instead-- but if they are similar in one respect, there should be a hidden folder in the user's $HOME directory containing the saved mount points to be remounted for that user. You could edit, or erase those. This being a KDE program, the program settings might be in ~/.kde/smb4k rather than just ~/.smb4k.
Alternatively, I see the program has a toolbar (thus is GUI), why not just unmount the shares within the program interface and either remount them with the correct settings, or mount nothing, and save those settings instead?
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