Header

awk -F: 'BEGIN {
    printf "%-10s %s\n", "User", "Home"
    printf "%-10s %s\n", "----","----"}
    { printf "%-10s %s\n", $1, $(NF-1) }
' /etc/passwd | head -n 5

Outputs

User       Home
----       ----
root       /root
bin        /bin
daemon     /sbin