CFrame and for i,v script isn't working. A little help?

You're attempting to call a method in the podiums array that doesn't exist. I believe you meant to get the CFrame of v

local podiums = game.Workspace.podiums:GetChildren()

script.Parent.MouseButton1Click:Connect(function()
    for i,v in pairs(podiums) do
        for i = 0,1,.001 do
        v:SetPrimaryPartCFrame(v:GetPrimaryPartCFrame()* CFrame.new(0,i,0))
        wait()
        end
    end
end)

#Edit You can use TweenService to animate the model going from one point to another.

local TweenService = game:GetService("TweenService")
local info = TweenInfo.new() -- # default tween info
local podiumsObject = game.Workspace.podiums
local podiumsTbl = {}
local properties = {
    ["CFrame"] = CFrame.new(0, 1, 0)

for i, v in ipairs(podiumsObject:GetChildren()) do
    table.insert(podiumsTbl, podiumsObject["podium" .. i])
end

for _, podium in ipairs(podiumsTbl) do
    local tween = TweenService:Create(
        podium.PrimaryPart, -- # instance to tween
        info, -- # tween info
        properties -- # properties dictionary 
    ) -- # create tween object for individual podiums
    tween:Play()
    tween.Completed:Wait() -- # wait for individual tween to complete 
end

info is just a default TweenInfo. Studios intellisense autocomplete should show the order of the arguments to pass so you can fiddle with those until you find a good fit.

What I do then is iterate over the children of podiums and insert them into podiumsTbl. podiumsObject["podium .. i"] is there to guarantee order from podium 1, podium2, etc. when iterating over podiumsTbl. properties is a dictionary whose keys will be the properties to tween and the values to tween to. So in this case it would tween the CFrame property to CFrame.new(0, 1, 0).

Also, as a side note, the proper terminology for "for i, v" is a generic for loop.