To adjust a misalignment in Photoshop, first click on File, then Print. In the Photoshop Print Settings there will be a section called Position and Size (different versions of Photoshop may have this section labeled differently).
To adjust the template's positioning, uncheck Center, then click in the Top or Left boxes. Positive numbers will move it down or right from a centered position, while negative numbers will move it up or left, respectively. By default, they will move by inches, however this can be changed in the Units option.
To adjust the template's scale, ensure Scale to Fit Media is unchecked, and adjust the percentage. For standard sheets, ensure that the Height and Width are set to 11 inches in Height and 8.5 inches in Width. For small sheets, ensure they are set to 6 inches in Height and 4 inches in Width.
Using decimals will create subtle adjustments for both position and scale.
Click Done to save any changes to your print settings, or Print to print your labels. After adjusting the template, do a test print on plain paper and line that up with your label sheet until you see that it is properly aligned.