The first thing to consider is the case of affine curves : let $k$ be an algebraically closed field, $C/k$ a smooth affine curve, $\bar{C}/k$ its smooth projective compactification, $\bar{C}=C\cup{p_0,p_1,...,p_n}$, $J=J(\bar{C})$ the jacobian, $\theta:C\rightarrow J$ the map induced by the choice of the base point $p_0$. Then $Pic^0(C)$ is identified with the quotient $J/\langle\theta(p_1),\ldots,\theta(p_n))\rangle$. This is always divisible but depends somehow on what this subgroup of the groups of rational points of an abelian variety look like (does it land in the torsion, etc.).
Let's think about it over $\mathbb{C}$ : there you have the quotient of a complex torus by a finitely generated subgroup : when this subgroup is not discrete the quotient does look like it is not representable as the $\mathbb{C}-$points of a scheme.
**Edit : ** As Emerton pointed out in the comments, in this case the correct "geometric" object is the 1-motive associated to C. But there is a general construction of Picard 1-motives associated to varieties over a field of characteristic 0 due to Barbieri-Viale and Srinivas, which encode the $Pic^0$ geometrically :
Albanese and Picard 1-motives Luca Barbieri-Viale - Vasudevan Srinivas Mémoires de la SMF 87 (2001), vi+104 pages