I got following error...
System.NullReferenceException: Object reference not set to an instance of an object. at Microsoft.SharePoint.SPListItem.get_UniqueId() at ConsoleApplication1.Program.Main(String[] args) in Program.cs:line 21
running following code
using (SPSite site = new SPSite("http://site/"))
{    
    using (SPWeb web = site.OpenWeb())
    {
        try
        {
            SPList list = web.Lists["ListName"]; // 2        
            SPListItem item = list.Items.Add();
            Guid itemId = item.UniqueId;
            SPListItem itemUpdate = web.Lists["ListName"].Items[itemId];
            itemUpdate["PercentComplete"] = .45; // 45%        
            itemUpdate.Update();
        }
        catch (Exception e)
        { 
            Console.WriteLine(e);
            Console.ReadLine();
        }
    }
}
What's the problem?
If you're trying to alter values for a just inserted list item, you should go with:
SPList list = web.Lists["ListName"];
//SPListItem item = list.Items.Add();
//item["PercentComplete"] = .45; // 45%
//item.Update();
SPListItemCollection items = list.GetItems(new SPQuery()
{
    Query = @"<Where>
                <Eq>
                   <FieldRef Name='Title' />
                   <Value Type='Text'>Desigining</Value>
                </Eq>
              </Where>"
});
foreach (SPListItem item in items)
{
    item["PercentComplete"] = .45; // 45%
    item.Update();
}
You just need to use list.Items[uniqueId] or faster list.GetItemByUniqueId(uniqueId) if you needs to find a particular item to update; what can be accomplished by using SPQuery class.
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