What is the effect of delaying smallpox post-exposure vaccination?

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Timing is the key here. After exposure, the body needs time to mount an immune response, and the vaccine works best when given as soon as possible. If vaccination is given promptly, it can intercept the virus as it begins to replicate, preventing illness or reducing its severity. Delaying vaccination lets the virus replicate longer before the immune response is boosted, so the vaccine is less able to prevent disease. So delaying vaccination lowers its effectiveness. It’s not that vaccination would be unnecessary with a delay, and it’s not more effective to wait; the benefit diminishes the longer you wait.