Nat64 requires a static route added to your gateway or each node, requires a custom DNS resolver and a daemon which manages iptables on a secondary gateway host for rewriting packets to/from IPv4 destination. It's pretty clever since it uses a /96 (32-bits) on the secondary gateway to return AAAA record for all IPv4 addresses.
Dual Stack is more straight forward requiring only an additional IPv6 address to be allocated to each machine requiring access.