No, not really. Emphasize is more general.
Accentuate is commonly used in art and beauty contexts - meaning enhance, to make something more beautiful, draw one's attention to something.
- She wears lipstick liner to accentuate the shape of her lips.
- The bright throw pillows accentuated the brown sofa.
- In your application, it is best to accentuate your positive characteristics.
- The spices, used in small measure, will accentuate the subtle taste of the dish.