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  1. Select the layer where the image resides
  2. Select the Alignment tool (Press the Q key to select this tool)
  3. Select the item/ image you want to align
  4. Press the Align center of target button and the Distribute vertical centers of targets button
  5. The image is should now be exactly center aligned

If you still need help with GIMP, be sure to check out the excellent GIMP 2.8 for Photographers book below.