Vagrantで複数ホストのセグメントを分けるには普通にサブネットを分けてIPを設定すればOKでした。

Vagrantfile

Vagrant.configure(2) do |config|

$script = <<EOF
    yum install wget
    yum -y install ibus-kkc vlgothic-*
    localectl set-locale LANG=ja_JP.UTF-8
    source /etc/locale.conf
EOF

    config.vm.define "chef-server" do |node|
        node.vm.box = "CentOS7.0"
        node.vm.hostname = "chef-server"
        node.vm.network :private_network, ip: "192.168.100.5"
        node.vm.network :private_network, ip: "192.168.101.10", :netmask => "255.255.255.0", virtualbox__intnet: "01"
        node.vm.provision :shell, :inline => $script
    end

    config.vm.define "chef-client01" do |node|
        node.vm.box = "CentOS7.0"
        node.vm.hostname = "chef-client01"
        node.vm.network :private_network, ip: "192.168.100.6"
        node.vm.network :private_network, ip: "192.168.101.11", :netmask => "255.255.255.0", virtualbox__intnet: "01"
        node.vm.network :private_network, ip: "192.168.102.20", :netmask => "255.255.255.0", virtualbox__intnet: "02"
        node.vm.provision :shell, :inline => $script
    end

    config.vm.define "chef-client02" do |node|
        node.vm.box = "CentOS7.0"
        node.vm.hostname = "chef-client02"
        node.vm.network :private_network, ip: "192.168.100.7"
        node.vm.network :private_network, ip: "192.168.102.21", :netmask => "255.255.255.0", virtualbox__intnet: "02"
        node.vm.provision :shell, :inline => $script
    end

end

メモ


#centos7取得
#box取得
vagrant box add CentOS7 https://github.com/tommy-muehle/puppet-vagrant-boxes/releases/download/1.1.0/centos-7.0-x86_64.box

#取得できたことを確認
vagrant box list

#作業ディレクトリで、初期化
vagrant init

#起動
vagrant up

#停止
vagrant halt

#一時停止、再開
vagrant suspend 
vagrant resume

#再起動
vagrant reload

#破棄
vagrant destroy

#boxを保存
vagrant package

#いいかんじのhost名をつける
vagrant ssh-config --host chefclient
vagrant ssh-config --host chefclient >> ~/.ssh/config