As a general rule, use maximum likelihood for your final tree. You may get a sense of the relationship with a preliminary neighbor joining tree but the tree will possibly differ if systematic bias is present. ML will correct that if the model of sequence evolution is the right one. A preliminary quick NJ tree is very useful for checking the quality of your data and its alignment. Any very very long branches suggest a good look at the data and the alignment to look for errors.
Let me know if you need help. Would be good to know more about your data set. How long are the sequences and how many sequences? What kind of phylogenetic software do you have access to?