I've been to chrome://net-internals/#dns and enabled IPV6 but there does not seem to be an option to have the browser try the IPV6 address first, it's defaulting to IPV4.
Before enabling IPV6 the default address family was: Default adress family: ADDRESS_FAMILY_IPV4 (IPv6 disabled) After enabling IPV6 it shows as: Default adress family: ADDRESS_FAMILY_UNSPECIFIED
This looked promising for a sec until it grabbed the IPV4 address first. Any help would be appreciated or even confirmation that it isn't possible.
IPv6 automatically gets a higher priority by default. RFC3484 describes the mechanism used for this. If you use 6to4 (2002::/16) then those IPv6 addresses will get a lower priority than IPv4. This is done because if your IPv6 connection depends on your IPv4 connection + the correct availability and working of several relays then you will probably have a better connection directly over IPv4. The same goes for Teredo (2001::/32).
If your system still connects over IPv4 even when you have native IPv6 connectivity then your IPv6 connectivity to that website is probably slow. There is a fail-safe built in in recent Chrome versions that tries IPv6 first, but when the connection hasn't been established within 300ms it tries to connect over IPv4 in parallel. This is done so that users with broken IPv6 connectivity are still able to reach dual stacked websites.
I hope this explains what you are seeing :)
Sander