Having played around with the settings, it looks as though my images are all aligned to the left from the outset – regardless of any changes I’ve made.
Changing the image height limit to 750px under Settings > Media in WP just reveals the issue, as it naturally reduces the width of some images to below the 950px preset width limit.
Previously, when I hadn’t specified the 750px height limit (and just left the 950px width limit) all images naturally touched both the left and right hand borders, and therefore appeared as if centered.
So the question is, how do I get the images below 950px in width to stop defaulting to the left?