Where do the two servers point for DNS. I'm guessing you have a registration problem. The first server points to itself for DNS. This doesn't seem a problem if you only have one domain controller. When you add the second, Clients attempt to log onto the second and are unable. The roots of this problem lie in service startup order, client name resolution order, and computer browser elections.
When a DC points to itself for DNS, the netlogon service attempts to start prior to DNS. That means that you don't get registered in DNS. Because this is the PDC emulator, it wins the browser election and becomes the master brouser. 2000 and XP clients try hosts, DNS, WINS, broadcast, lmhosts. Prior NT, 98, and 95 clients use lmhosts, wins, broadcast, dns, hosts name resolution order. 2000 and XP clients in such an environment would be noticably slower. Direct hosting of SMB over port 445 relies on being able to access the SRV record. In such an environment there would be no direct hosting, just downlevel RPC 135, 138 and 139 traffic.
When you add the second DC, it points to the first DC and does register in DNS. 2000 and XP clients will resolve the second DC only because the first is not registered in DNS, and DNS is first in the name resolution order.
To fix the problem you can do a couple of things. A sort of immediate workaround is to restart the netlogon service, ipconfig /registerdns, and nbtstat -RR on the first DC. This will resgister the first DC now that DNS has already started. The problem with this approach is that it needs to be done every time the DC is restarted.
A better way is, after initial replication, point the DCs at each other for DNS. Make your DNS zones AD integrated. Then, no matter what the state of any DC, each DC will always register with DNS and replicate the registration to the other DC.